JP3427755B2 - Method for producing silica-based membrane coated article - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an article in which the surface of a substrate such as glass, ceramics, plastics or metal is coated with a silica-based film, a silica-based film-coated article, and a liquid composition for silica-based film coating. , 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 a functional coating is provided on the surface of glass or other base material, it is necessary to improve the bonding strength between the base material and the functional coating, and when the base material contains an alkali component, diffusion of the alkali component. For the purpose of preventing the above and enhancing the durability performance of the functional film, various techniques are known in which a silica or other oxide underlayer film is provided between the base material and the functional film.

As a method of providing this oxide base film,
Sol-gel method (Japanese Patent Publication No. 4-20781, JP-A-2-3)
11332), and a method of applying a solution in which chlorosilane is dissolved in a non-aqueous solvent (JP-A-5-86353, JP-A-2525536 (JP-A-5-238781).
No.)), a CVD method, a vapor deposition method and the like are known.

[0004]

In these methods, the main object 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 group on the surface of the base film easily adsorbs water contained in the air, and once water is adsorbed, it is difficult to remove it easily.
Whether heating is performed to a certain degree (Japanese Patent Publication No. 4-20781, Japanese Patent Application Laid-Open No. 2-311332, Japanese Patent Application Laid-Open No. 5-2387).
No. 81), or even when heating is not necessary, a long-time treatment (the above-mentioned JP-A-5-86353) is required.

Further, a method for forming an oxide base film (Japanese Patent Laid-Open No. 2-311332, Japanese Patent No. 25255).
No. 36), the strength of the base film itself is low only by coating at room temperature.
Firing at about 00 to 600 ° C was indispensable. Further, when the base material contains an alkali, it is necessary to form an oxide underlayer 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 becomes large, there is a problem that the film thickness tends to become nonuniform, appearance defects such as uneven reflection are likely to occur, and the manufacturing cost increases.

Further, a method of applying a solution in which tetrachlorosilane is dissolved in a non-aqueous solvent such as perfluorocarbon, methylene chloride or hydrocarbon (the above Japanese Patent No. 252).
No. 5536), a silica underlayer can be obtained at room temperature, but the scratch resistance is low. The chlorosilyl group is extremely reactive and it is necessary to prepare and store the coating solution in an environment containing no water, which is not preferable from the viewpoint of manufacturing cost.

The present invention solves the above-mentioned problems of the prior art, and does not require a treatment such as firing that leads to an increase in manufacturing cost, and has an excellent silica-based film-coated article as a base film and excellent durability. An object of the present invention is to provide a method for easily producing a film-coated article in a short time.

[0008]

In order to solve the above problems, in the present invention, an alcohol solution consisting of a low concentration silicon alkoxide and a high concentration volatile acid is applied to a substrate and dried at room temperature. By coating the surface of the substrate with a silica-based film that is strong and has an alkoxyl group on the surface, and by 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 base material.

That is, the present invention provides a method for producing a silica-based film-coated article, which comprises applying a coating solution consisting of an alcohol solution containing a silicon alkoxide and an acid to a substrate, wherein the coating solution is (A) silicon alkoxide and its hydrate. At least one of decomposition products (including partial hydrolysis products) 0.010 to 3 wt% (silica conversion), (B) acid 0.0010 to 1.0 N, and (C) water 0 to 10 weight %, And a method for producing a silica-based film-coated article, which comprises: When the component (A) contains both a silicon alkoxide and its hydrolyzate (including a partial hydrolyzate), the weight% of the component (A) is the total value.

In the present invention, the silicon alkoxide used in the coating solution is not particularly limited, and examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like, which have a relatively high molecular weight. A small silicon alkoxide, for example, a tetraalkoxysilane having an alkoxyl group having 3 or less carbon atoms is preferably used because it tends to form a dense film. Polymers of these tetraalkoxysilanes having an average degree of polymerization of 5 or less are also preferably used.

The type of the acid catalyst used in the above coating solution is volatile such as hydrochloric acid, hydrofluoric acid, nitric acid, acetic acid, formic acid, trifluoroacetic acid, etc. from the viewpoint that it volatilizes upon drying at room temperature and does not remain in the film. Acids are preferred, and among them, hydrochloric acid, which has high volatility and is relatively easy to handle, is particularly preferred.

The alcohol solvent used in the coating liquid is not particularly limited, but examples thereof include methanol, ethanol, 1-propanol and 2-
Propanol, butyl alcohol, amyl alcohol and the like can be mentioned. Among them, methanol,
Chain saturated monohydric alcohols having a carbon number of 3 or less, such as ethanol, 1-propanol and 2-propanol, are preferably used because they have a high evaporation rate at room temperature.

Inside a coating liquid consisting of an alcohol solution containing a silicon alkoxide, an acid, and water (for dissolving the acid, impurities in the solvent, entering from the humidity of the atmosphere, etc.), during its preparation, during 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.

[Formula 1] (-Si-OR) + (H 2 O) → (-Si-OH) + (ROH) ····· (1)

The silanol group (-
Si-OH) forms a siloxane bond (-Si-O-Si-) by a dehydration condensation reaction as shown in formula (2).

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

As shown in the above formula (1), whether the alkoxy group of the silicon alkoxide undergoes a hydrolysis reaction in a coating solution consisting of an alcohol solution containing a silicon alkoxide, an acid and water, and the silanol which has undergone the hydrolysis reaction. Whether the groups (-Si-OH) undergo the dehydration condensation reaction as shown in the above formula (2) in the above coating liquid depends on the acid concentration of the solution, the concentration of the silicon alkoxide or its hydrolyzate, and the water content. Is greatly influenced by. As the silicon alkoxide concentration and water content are lower, the reaction of the above formula (1) is less likely to occur, and as a result, the reaction of the above formula (2) is less likely to occur, and the acid concentration of the solution is in the range of 0 to 3 at pH. In the case of, the reaction of the above formula (1) occurs quickly, but the reaction of the above formula (2) is difficult to occur.

In the present invention, the silicon alkoxide in the coating solution suppresses the above dehydration condensation reaction before the coating and keeps the polymerization degree as low as possible, and the coating solution is coated on the surface of the substrate and dried. At times, the reactions of the above formulas (1) and (2) are rapidly caused to form a siloxane bond, so that it is possible to form a dense film at room temperature. When the silicon alkoxide is hydrolyzed and polycondensed in a solution as in the prior art, voids are likely to occur because the polymer bonds to each other when the solution is applied to the surface of the substrate and dried, resulting in a dense structure. Baking and curing were necessary to obtain a dense film instead of a film. Therefore,
In the present invention, the silicon alkoxide in the coating liquid and its hydrolyzate (including partial hydrolyzate)
Is preferably a monomer or a polymer of less than 20-mer. However, when the total amount of the monomer and the polymer of less than 20-mer accounts for 80% by weight or more with respect to the entire silicon alkoxide and its hydrolyzate (including partial hydrolyzate), 20-mer or more It does not matter even if the polymer of is included.

In the present invention, by maintaining the concentration of the acid catalyst in the above coating liquid at 0.0010 to 1.0 N, the pH of the coating liquid becomes 0 to 3, particularly pH.
Is about 2, the hydrolysis reaction of the remaining alkoxyl groups 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 coating, and the coating liquid was applied. Immediately after that, these reactions rapidly proceed. The preferred concentration of acid in the coating solution is 0.01
~ 1.0 regulation.

The acid added as a catalyst preferably has a high concentration of 0.3 times or more the water content in order to maintain the concentration of the acid in the coating liquid. That is, when the acid in the form of an aqueous solution is used, it is preferable to use 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 0.5% by weight of water, the concentration of the acid in the ethanol solution is 0.15%.
It is preferable that the content is at least wt% (0.3 times 0.5 wt%), for example, at least 0.04 N for hydrochloric acid.

Further, silicon alkoxide and its hydrolyzate (including partial hydrolyzate) in the coating liquid.
The lower the total concentration of the above, the higher the pH of the coating solution, the more the hydrolysis reaction of the remaining alkoxyl groups of the formula (1) and the dehydration condensation reaction of the formula (2) before the coating are applied. It 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. The ability to prevent the diffusion of H2O3 tends to decrease and the durability performance tends to deteriorate, and when the 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 resulting silica film has a thickness of more than 300 nm, and the film is easily scratched and does not form a strong film. Therefore, the range of the total concentration of silicon alkoxide and its hydrolyzate (including partial hydrolyzate) in the coating liquid (including polymers less than 20-mer) 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.
When the concentration of is kept relatively high, the concentration of the acid catalyst in the coating solution is also preferably kept relatively high. Specifically, the coating liquid contains (A) silica equivalent, silicon alkoxide and its hydrolyzate (including a partial hydrolyzate) and (B) acid, in “(B)
It is preferable to contain the component (prescription) / (A) component (% by weight) "in an amount of 0.010 or more, more preferably 0.03 or more.

When a large amount of water is present in the coating liquid, the hydrolysis reaction of the silicon alkoxide is promoted in the liquid and the dehydration condensation reaction is likely to occur, and the film thickness is not uniform during the drying after coating the coating liquid. Therefore, the concentration of water in the coating solution is preferably as low as possible. Therefore, 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 way, the pH of the coating solution and the total concentration of silicon alkoxide and its hydrolyzate (including partial hydrolyzate) in the coating solution are maintained. Combined with this, the hydrolysis reaction of the remaining alkoxyl groups of the above formula (1) and the dehydration condensation reaction of the formula (2) are less likely to occur in the coating liquid before coating, which is preferable. Even if the concentration of water in the coating liquid is zero, the water content in the air is absorbed by the coating film after being coated on the base material, so that the hydrolysis reaction is not hindered. But,
Since a normal alcohol solvent originally contains a small amount of water, and the 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.

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

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

When the above coating liquid is applied to the substrate, the specific surface area of the applied liquid in a film form increases, so that the alcohol solvent in the film evaporates rapidly and the silicon alkoxide and its hydrolysis are formed. The total concentration of substances (including partial hydrolysates) in the coating film suddenly increased, and the hydrolysis and dehydration condensation reactions (the above 2
A further polycondensation reaction of a polymer of less than 0-mer occurs rapidly, and a large number of siloxane bonds (..Si-O-Si ..) are generated in the coating film. A highly dense film containing silica as a main component and having a film thickness of 5 to 300 nm and having a strong bond with the film is formed. As described above, in the present invention, the reactivity during film formation is high, the reaction is performed at room temperature to form a very dense film, and the subsequent firing is not necessary.

When many siloxane bonds due to dehydration condensation reaction already exist in the coating liquid before coating as in the prior art and a polymer having a degree of polymerization of 20 or more is contained in the coating liquid, the obtained silica film is Although the 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. Then, in order to strengthen this bond, firing at a higher temperature is conventionally required.

Furthermore, according to the present invention, since the hydrolysis reaction and dehydration condensation reaction of the partial hydrolyzed silicon alkoxide which has not been completely hydrolyzed in the coating solution 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 the functional film is coated thereon, the adhesiveness of the functional film is reduced. Can be improved. In order to form a dense silica film by the conventional sol-gel method, it is usually necessary to heat the dehydrated and condensed silica film at 500 to 600 ° C.

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

Whether or not the alkoxyl group remains on the surface of the silica film can be determined by measuring the static water droplet contact angle on the surface of the silica film. As will be shown in Examples later, 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 the silica film is densified by 5
When fired at 00 to 600 ° C, the value of the static water droplet contact angle is several degrees or less. In this way, the static water droplet contact angle becomes low because although the alkoxyl group remains on the silica film surface before firing, the alkoxyl group is decomposed by the above firing and the hydroxyl group on the silica film surface increases to make it hydrophilic. It is thought to be due to doing.

Even if a silica film having a hydroxyl group on the surface is used as a base film and a functional film liquid containing organosilane is applied onto the base film, the surface of the silica base film may be treated under normal circumstances before applying the organosilane. Water in the air is bound to the hydroxyl groups of and the water has been adsorbed on the surface of the base film,
Therefore, it becomes difficult to form a chemical bond between the silica base film and the organosilane at room temperature.

In the present invention, since many alkoxyl groups remain on the surface of the silica film and there are few hydroxyl groups, it is considered that moisture in the air is prevented from adsorbing on the surface of the base film. Therefore, when the functional film liquid containing organosilane is applied to this silica underlayer, the reaction between the alkoxyl group of the silica underlayer and the silanol group of organosilane (hydroxyl group or hydrolyzed functional group)
A chemical bond can be formed between the silica base film and the organosilane at room temperature, and the functional film can be firmly attached to the silica base film.

Oxide base, glass or ceramics,
Alternatively, even with respect to the surface of the hydrophilically-treated metal or plastics substrate, it is difficult to form a chemical bond between the applied organosilanes as it is as described above as it is. By forming the remaining silica base film on the surface of these base materials,
The functional film can be firmly attached to the base material. When this silica base film is heated to a high temperature, the remaining alkoxyl group disappears and a hydroxyl group is formed in its place, so when a functional film to be coated thereon is to be strongly adhered, The silica underlayer should not be preheated above 150 ° C.

Further, the silica film formed by the present invention has very excellent surface smoothness. Therefore, the functional film obtained by coating 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 mean roughness (Ra) of 0.5 nm or less, particularly 0.1.
0-0.5 nm, and ten-point average roughness (Rz) = 5.0
The roughness is less than or equal to nm, particularly 1.0 to 5.0 nm.
The surface roughness Ra and Rz are measured by an atomic force microscope (AF
M) (manufactured by Seiko Instruments Inc., scanning probe microscope “SPI3700”, cantilever; silicon “S”
I-DF20 ") is used to define the two-dimensional JIS
B 0601 can be measured by a three-dimensionally expanded 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 scan speed is 1.02 Hz, the surface shape is measured by DFM (cyclic contact mode), and the correction by the low pass filter is performed. The surface roughness Ra and Rz values were calculated by performing leveling correction of the measurement data (a curved surface was obtained by least-squares approximation and fitting was performed, the inclination of the data was corrected, and the distortion in the Z-axis direction was removed).

The functional film coated on the silica-based film according to the present invention exhibits excellent water repellency, excellent low friction resistance, excellent water drop rolling property, excellent antifouling property, and excellent durability. It is presumed that one of the reasons is due to the excellent smoothness of the surface of the functional film coated on the silica film having excellent smoothness. The reason why the silica film has excellent smoothness is presumed as follows. That is, in the coating liquid before coating, the silicon alkoxide is uniformly dissolved in the solvent in the form of a monomer (including a hydrolyzate) or a polymer of less than 20-mer, and after coating, It is speculated that due to the presence of a high concentration of the acid catalyst and the rapid increase of 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 liquid 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 increased. Since it is so high, 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 smoothness of the film is inferior to that of the present invention.

The above has described the article coated with a film made of a simple substance of silica, but the present invention can also be applied to the article coated with a film containing silica as a main component. That is, as a membrane component,
Silica-based multi-component oxide film obtained by adding an oxide other than silicon, such as aluminum, zirconium, titanium, or cerium, and substituting up to 30% by weight, usually 1 to 30% by weight, of the silica in terms of oxide. By
Further, the durability can be improved. Among them, aluminum and zirconium strengthen the base film itself,
Further, it is preferable because it strengthens the bond with the functional film.
If the amount of addition of oxides other than silicon is less than 1% by weight, the effect of addition will not be obtained, and if it is more than 30% by weight, the denseness of the film will be impaired and a strong film will not be obtained.

As for the addition of these oxides, it is preferable to add the alkoxide of these metals in the form of a chelate compound chemically modified with β-diketone, acetic acid, trifluoroacetic acid, ethanolamine and the like. In particular, when chemically modified with acetylacetone, which is a type of β-diketone, and added,
It is preferable because the stability of the solution is excellent and a relatively strong film is formed.

The silica-based film-coated article according to the present invention can be produced by using the above-mentioned coating solution containing an alcohol solution.
It is carried out by applying it to the surface of a substrate such as glass, ceramics, plastics or metal at room temperature and atmospheric pressure, and naturally or forcedly drying it at room temperature and atmospheric pressure or at a temperature of 150 ° C or lower for 30 seconds to 5 minutes. Be done.

Since a hydrophilic group such as a hydroxyl group is present on the surface of a substrate such as glass, ceramics or metal, a coating film is formed on the substrate when the above coating liquid is applied. However, depending on the type of the plastics base material, the surface thereof has few hydrophilic groups and poor wettability with alcohol, so that the coating liquid may be repelled on the surface of the base material, making 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 thereof is preliminarily treated with a plasma or corona atmosphere containing oxygen to make it hydrophilic, or the base material surface is exposed to 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 film coating treatment.

The method of applying the coating liquid for forming the silica-based film is not particularly limited, but for example, dip coating, flow coating, spin coating, bar coating, roll coating, spray coating, hand coating, brush. A coating method and the like can be mentioned.

According to the invention, glass, ceramics,
A dense and hard silica-based film can be formed on the surface of a base material such as metal or plastics 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-repellent, oil-repellent, anti-fogging, anti-fouling, low friction resistance by applying organosilane having functional functional group or its hydrolyzate (including partial hydrolyzate) or other coating. A functional film such as an antireflection optical film, a conductive film, a semiconductor film, or a protective film can be formed.

The hydrolyzable group of the organosilane is not particularly limited, but examples thereof include halogen, hydrogen, alkoxyl, acyloxy and isocyanate. In particular, an alkoxyl group is preferable because the reaction is not extremely vigorous 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 an organosilane containing a fluoroalkyl group as a water-repellent functional group and a hydrolyzable group is used. The method of treatment is preferred.

Organosilanes containing fluoroalkyl groups 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 and 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 trialkoxysilane 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 triacyloxysilane 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
Examples thereof include perfluoroalkyl group-containing triisocyanate silanes such as O) ₃ .

Further, by treating with an organosilane having 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.

Organosilanes 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
H ₃ ) ₃ SiCl-containing alkyl group-containing chlorosilanes;
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 SiOC ₂ H ₅ Alkyl group-containing alkoxysilanes 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
An alkyl group-containing acyloxysilane 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
Examples thereof include alkyl group-containing isocyanate silanes such as H ₃ ) ₂ Si (NCO) ₂ and (CH ₃ ) ₃ SiNCO.

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

As the above polyalkylene oxide group,
A polyethylene oxide group and a polypropylene oxide group 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. , N- (trichlorosilylpropyl) -O-polyethylene oxide urethane, and more specifically, [methoxy (polyethyleneoxy) propyl] trimethoxysilane and [methoxy (polyethyleneoxy) propyl] tri. Ethoxysilane, [butoxy (polypropyleneoxy)
Propyl] trimethoxysilane and the like are preferably used.

By dissolving a solution of these organosilanes in an alcohol solvent and hydrolyzing them using an acid catalyst on the silica-based film (base film), the surface of the base film can be treated without heat treatment. The dealcohol reaction between the alkoxyl group and the silanol group of the organosilane occurs, and the base film and the organosilane are bonded via the 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, etc., silanol and a trace amount present together with an alkoxyl group on the surface of the underlying film. By reacting with water, a bond between the undercoat film and the organosilane is formed, so the above organosilane can be applied as it is without dilution, or it can be used as a perfluorocarbon, methylene chloride, hydrocarbon, or silicone. You may apply the liquid only diluted with the non-aqueous solvent. By using the silica-based film having the alkoxyl group remaining on the surface as the base film, the functional film can be firmly attached to the substrate.

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

[0051]

Embodiments of the present invention will be described below.

[Example 1] To 98.6 g of ethanol (manufactured by Nacalai Tesque), 0.4 g of tetraethoxysilane (manufactured by Shin-Etsu Silicone) and 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 (silica conversion), hydrochloric acid and water in this treatment liquid are as shown in Table 1.

Then, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si
1 g of (OCH ₃ ) ₃ (heptadecafluorodecyltrimethoxysilane, made by Toshiba Silicone) was dissolved in 98 g of ethanol, 1.0 g of 0.1N hydrochloric acid was further added, and the mixture was stirred for 1 hour to obtain a water repellent treatment agent. It was

Washed soda lime silicate glass substrate (3
(00 × 300 mm) at a humidity of 30% and room temperature, the above-mentioned silica film treatment liquid was applied by a flow coating method and dried in about 1 minute to coat 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 with a pencil hardness, the film was not damaged even if the film was scratched with a pencil having an "H" core. In addition, the above-mentioned silica membrane treatment liquid is about 10
Exactly the same result was obtained even if it was used for a day and then used.

After that, 3 ml of the above-mentioned water repellent treatment agent was applied to cotton cloth on the surface of the glass substrate coated with the silica film, and the excess water repellent treatment agent was wiped off with a new cotton cloth to repel water. A treated glass was obtained.

With respect to this water-repellent treated glass, a contact angle meter (CA-DT, manufactured by Kyowa Interface Science Co., Ltd.) was used to obtain a water drop weight of 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 Denshi Co., Ltd.) in the cyclic contact mode to measure the surface shape and calculate the surface roughness Ra and the Rz value. did. As friction test, by attaching a dry cloth to a reciprocating abrasion tester (manufactured by Shinto Kagaku), water-repellent film surface under a load of 0.3 kg / cm ² 3
After sliding back and forth 000 times, the contact angle was measured. The contact angle on the surface of the silica film before coating the water repellent was also measured for reference. The contact angle of the clean glass substrate itself is about several degrees or less. The results of these measurements are shown in Table 2.

Before and after the friction test, the surface of the water-repellent film was visually observed to determine the presence or absence of unevenness of the film. In Table 2, when there is no unevenness of the film, "OK" is given, and when unevenness of the film is caused, "NG" is given. , "Respectively. As shown in Table 2, the contact angle on the surface of the silica film 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 and Rz = 2.9 nm, and the roughness of the film surface after the water repellent treatment is Ra = 0.3 nm and Rz = 2.8.
was nm. The roughness of the film surface of the cleaned soda lime silicate glass substrate before coating the silica film is Ra =
It was 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 Kasei) was used instead of tetraethoxysilane used in the preparation of the silica film treating solution in Example 1. I got a glass. The composition of the silica film treatment liquid is shown in Table 1, and the silica film thickness, various contact angles, surface roughness, etc. are shown in Table 2. 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 and Rz = 2.
8 nm, and the roughness of the film surface after the water repellent treatment is Ra =
It was 0.3 nm and Rz = 2.7 nm.

[Example 3] A water-repellent treated glass was obtained in the same manner as in Example 1 except that the coating of the silica film treating liquid was changed to the spray method. As shown in Table 2, the contact angle of the silica film surface before applying the water repellent agent 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 and Rz = 3.0n.
m, and the roughness of the film surface after the water repellent treatment is Ra = 0.4.
nm and Rz = 2.9 nm.

[Example 4] 64.8 g of ethanol, 9.8 g of acetylacetone, and aluminum-tri-sec.
-Butoxide (manufactured by Kanto Kagaku Co., Ltd.) (25.4 g) 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 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 film treatment liquid.

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 liquid was used in place of the silica treating liquid of Example 1. Silica film thickness,
Table 2 shows various contact angles and surface roughness. 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 is Ra = 0.4 nm and Rz = 3.3 nm, and the film surface roughness after the water repellent treatment is Ra = 0.4 nm and Rz =.
It was 3.0 nm.

Example 5 Ethanol (78.6 g) was mixed with acetylacetone (4.1 g) and zirconium-tetra-n-.
Butoxide (manufactured by Kanto Kagaku Co., Ltd.) (17.4 g) was dissolved to obtain a zirconia raw material liquid (5% by weight in terms of oxide).

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

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 liquid was used in place of the silica film treating liquid of Example 1. Table 2 shows the thickness, various contact angles, surface roughness, etc. of the silica-based film. As shown in Table 2, the contact angle of the silica-based film surface before applying 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 is Ra = 0.4 nm and Rz = 3.4 nm, and the film surface roughness after the water repellent treatment is Ra = 0.4 nm and Rz =.
It was 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., Inc.) were mixed in the proportions shown in Table 3 to obtain a silica membrane treatment liquid. The composition of this silica film treatment liquid is shown in Table 1.

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

[Examples 10 to 13] CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (O) used for the preparation of the water repellent treatment liquid in Example 1
Instead of CH ₃ ) ₃ (heptadecafluorodecyltrimethoxysilane, manufactured by Toshiba Silicone Co., Ltd.), in Example 10, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ (tridecafluoro) was used. Octyltrimethoxysilane, manufactured by Toshiba Silicone Co., Ltd., was used in Example 11 as CF ₃ (CF ₂ ) ₃ (C
H ₂ ) ₂ SiCl ₃ (nonafluorohexyltrichlorosilane, manufactured by Chisso Corporation) was used as CF ₃ (C
H ₂ ) ₂ Si (OCH ₃ ) ₃ (trifluoropropyltrimethoxysilane, manufactured by Chisso) was used as CF in Example 13.
_A 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 abrasion 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
A water repellent and low friction resistance glass was obtained in the same manner as in Example 1 except that CH ₃ ) ₃ (heptadecafluorodecyltrimethoxysilane, manufactured by Toshiba Silicone) was replaced with alkylsilane. Table 4 shows the composition of the water-repellent and low-friction resistance film treating liquid.

The contact angles of these water-repellent and low-friction glasses were measured at the initial stage and after the friction test. Further, a dry cloth was attached to a wear coefficient measuring device (manufactured by Shinto Kagaku Co., Ltd.), and the friction coefficient between the film surface and the dry cloth was measured. The results of these measurements are shown in Table 5. 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 of 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.
As compared with No. 42, glass having a smaller friction coefficient was obtained.
The friction coefficient after the friction test was almost unchanged from that before the friction test.

[Example 19] CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC) used in the preparation of the water repellent treatment liquid in Example 1
H ₃ ) ₃ (heptadecafluorodecyltrimethoxysilane, manufactured by Toshiba Silicone) is [methoxy (polyethyleneoxy) propyl] trimethoxysilane (manufactured by Chisso Corporation, content 90%, molecular weight 460-590, ethylene oxide unit number 6- In the same manner as in Example 1 except that 9) was replaced, the critical inclination angle at which water droplets started rolling was low, and
A functional film was obtained in which dirt was not easily absorbed or attached.

The contact angle of the functional film was 38 degrees. The critical tilt angle, which is a measure of the ease with which water droplets roll, is obtained by arranging the obtained functional film-treated glass sample horizontally, placing water droplets with a diameter of 5 mm on it, and gradually inclining the glass plate. It was 4 degrees as determined by measuring the angle of inclination from the horizontal when the water droplets started to roll, and a surface on which the water droplets rolled very easily was obtained. Furthermore, the contact angle after the friction test was 38 degrees, and the critical tilt angle after the friction test was 4 degrees, and almost the same performance as before the friction test was maintained.

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

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above silica film treating liquid was used in place of the silica film treating liquid of Example 1. Silica film thickness,
Table 2 shows various contact angles and surface roughness. As shown in Table 2, the contact angle of the silica film surface before applying the water repellent is 2
The initial contact angle after water repellency treatment was 9 °, 105 °, and the contact angle after friction test was 60 °, which shows that the water repellency after the friction test is deteriorated. 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. Both Rz of silica film and water repellent film are 5.0n
Since it exceeds m, it can be seen that the smoothness of the film is inferior.

[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, and a silica membrane treatment liquid Got The composition of this silica film treatment liquid is shown in Table 1.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above silica film treating liquid was used in place of the silica film treating liquid of Example 1. Silica film thickness,
Table 2 shows various contact angles and surface roughness. As shown in Table 2, the contact angle of the silica film surface before applying the water repellent is 2
The initial contact angle after water-repellent treatment was 5 °, 110 °, and the contact angle after friction test was 80 °, which shows that the water-repellent performance after friction test is deteriorated. The surface roughness of the silica film is Ra =
It was 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. Both Ra and Rz of the silica film and the water-repellent film exceeded 0.5 nm and 5.0 nm, respectively, indicating that the smoothness of the film was poor. In addition, 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 0.1N hydrochloric acid were added with stirring to prepare a silica film treating solution. Got The composition of this silica film treatment liquid is shown in Table 1.

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

COMPARATIVE EXAMPLE 4 89.6 g of ethanol (manufactured by Nacalai Tesque), 0.4 g of tetraethoxysilane (manufactured by Shin-Etsu Silicone) and concentrated hydrochloric acid (35% by weight, manufactured by Kanto Kagaku)
20 g was added with stirring to obtain a silica membrane treatment liquid.
The composition of this silica film treatment liquid is shown in Table 1.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above silica film treating liquid was used in place of the silica film treating liquid of Example 1. Table 2 shows the thickness, various contact angles, surface roughness, etc. 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, and the contact angle after the friction test was 87 degrees. It can be seen that the water repellency performance of is decreased. In addition, the obtained film had unevenness in film thickness. 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, both exceeded Ra = 0.5 nm and Rz = 5.0 nm, and the smoothness of the film surface was poor.

[Comparative Example 5] 0.46 g of tetraethoxysilane (manufactured by Shin-Etsu Silicone) and 29.6 g of ethanol (manufactured by Nacalai Tesque) and a methanol solution of hydrochloric acid (10% by weight,
70 g of Tokyo Kasei) was added with stirring to obtain a silica membrane treatment liquid. The composition of this silica film treatment liquid is shown in Table 1.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above silica film treating liquid was used in place of the silica film treating liquid of Example 1. Table 2 shows the thickness, various contact angles, surface roughness, etc. 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, and the contact angle after the friction test was 88 degrees. It can be seen that the water repellency performance of is decreased. In addition, the obtained film had unevenness in film thickness. The surface roughness of the silica film is Ra = 0.7n
m, Rz = 8.8 nm, the roughness of the film surface after the water repellent treatment is
Ra = 0.7 nm and Rz = 7.8 nm, and both exceeded Ra = 0.5 nm and Rz = 5.0 nm, and the smoothness of the film surface was poor.

Comparative Example 6 In 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. The composition of this silica film treatment liquid is shown in Table 1.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above silica film treating liquid was used in place of the silica film treating liquid of Example 1. Table 2 shows the thickness, various contact angles, surface roughness, etc. 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, and the contact angle after the friction test was 86 degrees. It can be seen that the water repellency performance of is decreased. In addition, the obtained film had unevenness in film thickness. The surface roughness of the silica film is Ra = 0.6n.
m, Rz = 9.8 nm, the roughness of the film surface after the water repellent treatment is
Ra = 0.7 nm and Rz = 10.8 nm, and both exceed Ra = 0.5 nm and Rz = 5.0 nm.
The smoothness of the film surface was poor.

[Comparative Example 7] A hydrolyzate of ethyl silicate (average degree of polymerization: about 5) (average molecular weight: 408.5, "HAS-1") was added to 96 g of ethanol (produced by Nacalai Tesque).
0 ", manufactured by Colcoat Co., Ltd., silica content 10% by weight) 4 g was mixed to obtain a silica membrane treatment liquid. The composition of this silica film treatment liquid is shown in Table 1. This silica membrane treatment liquid was flow-coated on a washed glass substrate (300 × 300 mm) at a humidity of 30% and room temperature, and dried in about 1 minute. Then, the substrate was baked 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 film was scratched when the film was scratched with the pencil of the "B" core. The silica film after firing was not damaged even if the film was scratched with a pencil having an "H" core.

Further, this silica film-covered glass was subjected to ultrasonic cleaning in pure water for 10 minutes, dried and then 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 is 2 degrees,
The initial contact angle after the water repellent treatment is 106 degrees, and the contact angle after the friction test is 50 degrees, which shows that the water repellent performance after the friction test is significantly reduced. The surface roughness of the silica film is Ra =
0.9 nm, Rz = 12.1 nm, and the roughness of the film surface after the water repellent treatment is Ra = 0.8 nm and Rz = 10.3 nm, both exceeding 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 respectively. 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, but the contact angle after the friction test was 55 degrees, and for the glass of Example 15 Value (90 degrees) was significantly lower, and the film was inferior in abrasion resistance. The coefficient of friction after the friction test was 0.45, and the low friction resistance function was lost due to friction.

[Comparative Example 9] A water repellent and low friction 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 carried out. 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 tilt angle was 25 degrees, and the contact angle decreased and the critical tilt angle increased remarkably, and the wear resistance was poor.

[0089]

[Table 1] ================================= tetraalkoxysilane aluminum trisilconium tetrahydrochloric acid water butoxybutoxide (SiO 2 ₂ conversion) (Al ₂ O ₃ conversion) (ZrO ₂ conversion) (wt%) (wt%) (wt%) (normative) (wt%) −−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−− 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 film Water repellent glass           Film thickness Contact angle Surface roughness Initial surface 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 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 / 3.3 106 104 104 0.4 / 3.0 OK Example 5 35 29 0.4 / 3.4 107 103 0.4 / 3.2 OK Example 6 15 28 0.4 / 3.2 106 93 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 Same as above 101 90 0.3 / 2.8 OK Example 12 〃 〃 〃 95 88 0.3 / 2.8 OK Example 13 〃 〃 〃 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 / 9.8 107 107 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 / 9.8 109 109 86 0.7 / 10.8 NG Comparative Example 7 40 2 0.9 / 12.1 106 106 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-octadecyltrimethoxysilane 1 1 98 Example 15 n-Dodecyltrimethoxysilane 1 1 98 Example 16 n-Octyltriethoxysilane 1 1 98 Example 17 n-pentyltriethoxysilane 1 1 98 Example 18 Trimethylethoxysilane 1 1 98 ================================

[0093]

[Table 5] −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−           Initial contact angle Initial friction coefficient Contact angle after friction test Friction coefficient after friction test             (Degree) (degree) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 14 95 0.23 94 0.24 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 15 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]

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

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Sunada, 3-5-11 Doshumachi, Chuo-ku, Osaka, Japan Nihon Sheet Glass Co., Ltd. (72) Hiroaki Kobayashi 3-5-11, Doshumachi, Chuo-ku, Osaka No. Nippon Sheet Glass Co., Ltd. (72) Inventor Hiroaki Yamamoto 3-5-11 Doshomachi, Chuo-ku, Osaka City No. 11 Nihon Sheet Glass Co., Ltd. (72) Inventor Eiji Ogawa 3-5, Doshucho, Chuo-ku, Osaka City No. 11 Within Nihon Sheet Glass Co., Ltd. (56) Reference JP-A-4-338137 (JP, A) JP-A-5-345641 (JP, A) JP-A-7-138046 (JP, A) JP-A-3 -211285 (JP, A) JP 5-302173 (JP, A) JP 8-337753 (JP, A) JP 9-71438 (JP, A) JP 5-238781 (JP, A) ) JP-A-7-311130 (JP, A) JP-A-6- 53647 (JP, A) JP-A-6-41761 (JP, A) JP-A-59-195504 (JP, A) JP-A-9-142888 (JP, A) JP-A-9-132433 (JP, A) JP-A-11-71682 (JP, A) International Publication 99/28534 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23C 18/12 B05D 7/24 302 C03C 17/30 H01L 21/316 C08J 7/06

Claims (27)

(57) [Claims] 1. A method for producing a silica-based film-coated article, which comprises applying a coating liquid comprising an alcohol solution containing a silicon alkoxide and an acid to a substrate, wherein the coating liquid is (A) silicon alkoxide and its hydrolyzate ( (Including a partial hydrolyzate) 0.010 to 3% by weight (silica conversion), (B) acid 0.0010 to 1.0 N, and (C) water 0 to 10% by weight, A method for producing a silica-based film-coated article, which comprises: 2. The coating liquid comprises at least one of silicon alkoxide and its hydrolyzate (including a partial hydrolyzate) in terms of (A) silica.
The silica-based film-coated article according to claim 1, wherein the silica-based film-coated article contains the acid and the component (B) so that the ratio of “(B) component (normative) / (A) component (wt%)” is 0.010 or more. Method. 3. The coating liquid contains the (B) acid and (C) water such that [(B) component (normative) × (C) component (wt%)] 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 its hydrolyzate (including partial hydrolyzate) 0.010 to 0.6% by weight (silica conversion); ) Acid 0.010-1.0 normal, and (C) Water 0-2 weight% is contained, The method of manufacturing the silica film | membrane coated article in any one of Claims 1-3. 5. The coating liquid has a water content of 0.
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 of 3 times or more and a silicon alkoxide are dissolved in 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 of making 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 substituted silica-based film-coated article according to any one of claims 1 to 6. 8. The method for producing a silica-based film-coated article according to claim 7, wherein the β-diketone of the ligand is acetylacetone. 9. The method for producing a silica-based film-coated article according to claim 7, wherein the metal alkoxide is an alkoxide of aluminum or zirconium. 10. The method for producing a silica-based film-coated article according to claim 1, wherein the coating liquid has a pH of 0-3. 11. The method for producing a silica-based film-coated article according to claim 1, wherein the film of the coating liquid applied to the substrate is dried at room temperature or a temperature of 150 ° C. or lower. 12. The method for producing a silica-based film-coated article according to claim 11, wherein the coating liquid is applied to the surface of the base material so that the applied film has a thickness after drying of 5 to 300 nm. 13. The method for producing a silica-based film-coated article according to claim 1, wherein the base material is a transparent glass plate. 14. A silica-based film-coated article having a static water droplet contact angle of 20 to 40 degrees, which is obtained by the method according to any one of claims 1 to 13. 15. Arithmetic mean roughness (Ra) of the surface obtained by the method according to claim 1.
A silica-based film-coated article of 0.10 nm or more and 0.5 nm or less and a ten-point average roughness (Rz) = 1.0 nm or more and 5.0 nm or less. 16. A surface of a silica-based film-coated article obtained by the method according to any one of claims 1 to 13,
A method for producing a functional film-coated article, which comprises applying a composition for a functional film. 17. The functional film composition contains at least one of an organosilane having a hydrolyzable functional group and a functional functional group, and a hydrolyzate thereof (including a partial hydrolyzate). A method for producing the functional film-coated article according to claim 16 . 18. The method for producing a functional film-coated article according to claim 17 , wherein the hydrolyzable functional group is an alkoxyl group. 19. The method for producing a functional film-coated article according to claim 16, wherein the functional film composition is a water-repellent film forming composition. 20. The water-repellent film-forming composition contains at least one of an organosilane containing an alkoxyl group and a fluoroalkyl group in the molecule and a hydrolyzate thereof (including a partial hydrolyzate). Item 20. A method for producing the functional film-coated article according to Item 19 . 21. The method for producing a functional film-coated article according to claim 16, wherein the composition for functional film is a composition for forming a water repellent and low friction resistance film. 22. The water-repellent and low-friction resistance film-forming composition comprises at least one of an organosilane containing an alkoxyl group and an alkyl group in the molecule and a hydrolyzate thereof (including a partial hydrolyzate). Claim 2 including
A method for producing the functional film-coated article according to 1 . 23. The method for producing a functional film-coated article according to claim 16, wherein the functional film composition is a film-forming composition having excellent water drop rolling properties and antifouling properties. 24. excellent rolling resistance of the water droplet, and anti-film forming composition that having a fouling property, organosilanes and hydrolysates thereof containing an alkoxyl group and a polyalkylene oxide group in the molecule (partial The method for producing a functional film-coated article according to claim 23 , comprising at least one of (including a hydrolyzate). 25. A functional film-coated article obtained by the method according to any one of claims 16 to 24 . 26. A functional film-coated article obtainable by the method according to claim 16 .
The surface of the coating has an arithmetic mean 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. 27. (A) Silicon alkoxide and its hydrolysates (including partial hydrolysates) At least one                         0.010 to 3% by weight (silica conversion), (B) acid 0.0010 to 1.0 N, (C) 0 to 10% by weight of water,and (D) Alcohol balance A silica-based film coating liquid composition comprising: