JP2000336334A - Production of silicaceous film-coated article and functional film-coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for readily producing an article coated with a siliceous film excellent as a ground film and an article coated with a functional film excellent in durability in a short time. SOLUTION: An acid and water are contained in a coating liquid so as that the acid/water weight ratio is >=0.58 and the acid is obtained by dissolving a hydrogen halide in an alcohol solvent in a method for producing a siliceous film-coated article comprising coating a substrate with the coating liquid containing a silicon alkoxide and the acid in the alcohol solvent.

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 base film easily adsorb water contained in the air, and it is difficult to remove water once it is adsorbed.
C. or about (Central Japanese Patent Publication No. 4-20781,
JP-A-2-313332, JP-A-5-238
No. 781) 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, the film thickness tends to be non-uniform, and appearance defects such as reflection unevenness are likely to occur.
There were problems such as an increase in manufacturing cost.

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 the preparation and storage of the coating solution must be performed in an environment containing no water, which is not preferable from the viewpoint 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]

According to the present invention, there is provided a method for producing a silica-based film-coated article in which a coating liquid containing a silicon alkoxide and an acid in an alcohol solvent is applied to a substrate, wherein the coating liquid comprises the acid and the acid. Producing a silica-based membrane-coated article, wherein water is contained so that the weight ratio of acid / water is 0.58 or more, and the acid is obtained by dissolving hydrogen halide in the alcohol solvent. How to

In the present invention, as the silicon alkoxide used in the coating solution, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane,
Tetrabutoxysilane and the like can be mentioned. Among these, those having a relatively small molecular weight, for example, a tetraalkoxysilane having an alkoxyl group having 3 or less carbon atoms are preferably used because a dense film is easily formed. Further, a polymer of these tetraalkoxysilanes having an average degree of polymerization of 5 or less may be used.

In the present invention, the acid and water contained in the coating solution are adjusted so that the weight ratio of acid / water is 0.58 or more. Acid / water weight ratio of 0.58
By keeping the above, in the coating solution before application,
A hydrolysis reaction and a dehydration condensation reaction of a hydrolyzate of a silicon alkoxide are suppressed, and the occurrence of unevenness in film thickness during drying after application of a coating liquid is prevented. As a result, the obtained film becomes strong with excellent denseness.

As the kind of the acid catalyst in the present invention, hydrohalic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, and hydrofluoric acid are used from the viewpoint that they are volatilized by drying at room temperature and do not remain in the film. Hydrochloric acid, which is used and has high volatility and is relatively safe in handling, is particularly preferred. As these acids, those which do not contain water are used, and hydrogen halides such as hydrogen chloride, hydrogen bromide, hydrogen iodide and hydrogen fluoride are dissolved in the alcohol solvent of the coating liquid. This makes it easy to maintain the weight ratio of acid / water in the coating liquid to 0.58 or more. If hydrochloric acid, hydrobromic acid, or hydroiodic acid in the form of an aqueous solution is used, the water contained therein will be mixed into the coating solution, and the weight ratio of acid / water in the coating solution will be considered. Is not easily maintained at 0.58 or more.

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. In addition, in order to control the amount of water added, a solvent which has been subjected to a dehydration treatment to reduce the water content to, for example, 0.005% by weight or less may be used.

[0013] In addition to the silicon alkoxide and the acid, the coating liquid according to the present invention may be, for example, a small amount of methyltrialkoxysilane, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxy. Silane is converted to silica, and the silicon alkoxide content of 50
It can be contained in an amount of up to% by weight.

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

In addition, 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 composed of 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, before coating, the silicon alkoxide in the coating solution suppresses the above-mentioned dehydration-condensation reaction and keeps the polymerization degree as low as possible. This coating solution is applied to the surface of the substrate and dried. Occasionally, the reactions of the above formulas (1) and (2) are suddenly caused 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 tends to be bonded to each other when the solution is applied to the surface of the substrate and dried. Does not become
Firing and curing were necessary to obtain a dense film. Therefore, in the present invention, the silicon alkoxide and its hydrolyzate (including partial hydrolyzate) in the coating liquid are 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 maintaining the concentration of the acid catalyst in the coating solution at 0.0010 to 3.0 normality, the hydrolysis reaction of the remaining alkoxyl group in the above formula (1) and the above formula (2) The dehydration-condensation reaction of (1) becomes difficult to occur in the coating liquid before application, and these reactions rapidly proceed immediately after the application of the coating liquid. The preferred concentration of the acid in the coating solution is 0.01 to 1.5 normal.

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 to include the “component (defined) / (A) component (% by weight)” so as to 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 weight ratio of acid / water in the coating solution becomes less than 0.58, so that the hydrolysis reaction of silicon alkoxide is promoted in the solution and the dehydration condensation reaction It is preferable that the concentration of water in the coating solution be as small as possible, since the film thickness tends to be uneven and the thickness of the coating solution tends to be uneven during drying after application of the coating solution. 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.

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.

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 the polycondensation reaction of a polymer of less than 0-mer) rapidly occurs, and a large number of siloxane bonds (..Si-O-Si ..) are generated in the coating film. And a highly dense film mainly composed of silica having a thickness of 5 to 300 nm is formed. 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, in order to strengthen this bond, firing at a higher temperature is required.

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.

While the above description has been made with reference to a film-coated article made of silica alone, the present invention can also be applied to a film-coated article mainly composed 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 an 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 liquid comprising the above-mentioned alcohol solution is used.
The coating is performed by applying to the surface of a base material such as glass, ceramics, plastics or metal at room temperature and normal pressure, and by natural drying or forced drying at room temperature and normal pressure or at a temperature of 150 ° C. or lower for 30 seconds to 5 minutes. Will be

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. For example, dip coating, flow coating, spin coating, bar coating, roll coating, spray coating, hand coating, brushing 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 By applying an organosilane having a functional functional group, or a hydrolyzate thereof (including a partial hydrolyzate), or by performing other coating,
Water repellency, oil repellency, antifogging, antifouling, low friction resistance, antireflection, and other functional films such as 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 of 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.

Organo-containing fluoroalkyl group
As a run, CF_Three(CF_Two)₁₁(CH_Two)_TwoSiCl_Three,
CF_Three(CF_Two)_Ten(CH_Two)_TwoSi (Cl)_Three, CF_Three(C
F_Two)₉(CH_Two)_TwoSiCl_Three, CF_Three(CF_Two)₈(CH_Two)
_TwoSiCl _Three, CF_Three(CF_Two)₇(CH_Two)_TwoSiCl_Three, CF
_Three(CF_Two)₆(CH_Two)_TwoSiCl_Three, CF_Three(CF_Two)_Five(C
H_Two)_TwoSiCl_Three, CF_Three(CF_Two)_Four(CH_Two)_TwoSiC
l_Three, CF_Three(CF_Two)_Three(CH_Two)_TwoSiCl_Three, CF_Three(C
F_Two)_Two(CH_Two)_TwoSiCl_Three, CF_ThreeCF_Two(CH_Two)_TwoSi
Cl_Three, CF_Three(CH_Two)_TwoSiCl_ThreePerfluoro
Alkyl group-containing trichlorosilane; CF_Three(CF_Two)
₁₁(CH_Two)_TwoSi (OCH_Three)_Three, CF_Three(CF_Two)_Ten(C
H_Two)_TwoSi (OCH_Three)_Three, CF_Three(CF_Two)₉(CH_Two)_TwoS
i (OCH_Three)_Three, CF_Three(CF_Two)₈(CH_Two)_TwoSi (OC
H_Three)_Three, CF_Three(CF_Two)₇(CH_Two)_TwoSi (OCH_Three)_Three,
CF_Three(CF_Two)₆(CH_Two)_TwoSi (OCH_Three)_Three, CF
_Three(CF_Two)_Five(CH_Two)_TwoSi (OCH_Three)_Three, CF_Three(C
F_Two)_Four(CH_Two)_TwoSi (OCH_Three)_Three, CF_Three(CF_Two)
_Three(CH_Two)_TwoSi (OCH_Three)_Three, CF_Three(CF_Two)_Two(C
H_Two)_TwoSi (OCH_Three)_Three, CF_ThreeCF_Two(CH_Two)_TwoSi (O
CH_Three)_Three, CF_Three(CH_Two)_TwoSi (OCH_Three)_Three, CF
_Three(CF_Two)₁₁(CH_Two)_TwoSi (OC_TwoH_Five)_Three, CF_Three(C
F_Two)_Ten(CH_Two)_TwoSi (OC_TwoH_Five)_Three, CF_Three(CF_Two)₉
(CH_Two)_TwoSi (OC_TwoH_Five)_Three, CF_Three(CF_Two)₈(C
H _Two)_TwoSi (OC_TwoH_Five)_Three, CF_Three(CF_Two)₇(CH_Two)_Two
Si (OC_TwoH_Five)_Three, CF_Three(CF_Two)₆(CH_Two)_TwoSi (O
C_TwoH_Five)_Three, CF_Three(CF_Two)_Five(CH_Two)_TwoSi (OC
_TwoH_Five)_Three, CF_Three(CF_Two)_Four(CH_Two)_TwoSi (OC
_TwoH_Five)_Three, CF_Three(CF_Two)_Three(CH _Two)_TwoSi (OC
_TwoH_Five)_Three, CF_Three(CF_Two)_Two(CH_Two)_TwoSi (OC
_TwoH_Five)_Three, CF_ThreeCF_Two(CH_Two)_TwoSi (OC_TwoH_Five)_Three, C
F_Three(CH_Two)_TwoSi (OC_TwoH_Five)_ThreePerfluoro
Alkyl group-containing trialkoxysilane; CF_Three(CF_Two)
₁₁(CH_Two)_TwoSi (OCOCH_Three)_Three, CF_Three(CF_Two)_Ten
(CH_Two) _TwoSi (OCOCH_Three)_Three, CF_Three(CF_Two)₉(C
H_Two)_TwoSi (OCOCH_Three)_Three, CF _Three(CF_Two)₈(C
H_Two)_TwoSi (OCOCH_Three)_Three, CF_Three(CF_Two)₇(C
H_Two)_TwoSi (OCOCH_Three)_Three, CF_Three(CF_Two)₆(C
H_Two)_TwoSi (OCOCH_Three)_Three, CF_Three(CF_Two)_Five(C
H_Two)_TwoSi (OCOCH_Three)_Three, CF_Three(CF_Two)_Four(C
H_Two)_TwoSi (OCOCH_Three)_Three, CF_Three(CF_Two)_Three(C
H_Two)_TwoSi (OCOCH_Three)_Three, CF_Three(CF_Two) _Two(C
H_Two)_TwoSi (OCOCH_Three)_Three, CF_ThreeCF_Two(CH_Two)_TwoSi
(OCOCH_Three)_Three, CF_Three(CH_Two)_TwoSi (OCOC
H_Three)_ThreeSuch as perfluoroalkyl group-containing triacylo
Xysilane; CF_Three(CF_Two)₁₁(CH_Two)_TwoSi (NC
O)_Three, CF_Three(CF_Two)_Ten(CH_Two)_TwoSi (NCO)_Three,
CF_Three(CF_Two)₉(CH_Two)_TwoSi (NCO)_Three, CF_Three(C
F_Two)₈(CH_Two)_TwoSi (NCO)_Three, CF_Three(CF_Two)
₇(CH_Two)_TwoSi (NCO)_Three, CF_Three(CF_Two)₆(C
H_Two)_TwoSi (NCO)_Three, CF_Three(CF_Two)_Five(CH_Two)_TwoSi
(NCO) _Three, CF_Three(CF_Two)_Four(CH_Two)_TwoSi (NC
O)_Three, CF_Three(CF_Two)_Three(CH_Two)_TwoSi (NCO)_Three, C
F_Three(CF_Two)_Two(CH_Two)_TwoSi (NCO)_Three, CF_ThreeCF_Two
(CH_Two)_TwoSi (NCO)_Three, CF_Three(CH_Two)_TwoSi (NC
O)_ThreeSuch as perfluoroalkyl group-containing triisomers
An example silane can be given.

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.

As an organosilane containing an alkyl group,
The CH_Three(CH_Two)₃₀SiCl_Three, CH_Three(CH_Two)₂₀S
iCl_Three, CH_Three(CH_Two)₁₈SiCl_Three, CH_Three(CH_Two)₁₆
SiCl_Three, CH_Three(CH_Two)₁₄SiCl_Three, CH_Three(CH_Two)
₁₂SiCl_Three, CH_Three(CH_Two)_TenSiCl_Three, CH_Three(C
H_Two)₉SiCl_Three, CH_Three(CH_Two)₈SiCl_Three, CH_Three(C
H_Two)₇SiCl_Three, CH_Three(CH_Two)₆SiCl_Three, CH_Three(C
H_Two)_FiveSiCl_Three, CH _Three(CH_Two)_FourSiCl_Three, CH_Three(C
H_Two)_ThreeSiCl_Three, CH_Three(CH_Two)_TwoSiCl_Three, CH_ThreeCH
_TwoSiCl_Three, (CH_ThreeCH_Two)_TwoSiCl_Two, (CH_ThreeCH_Two)
_ThreeSiCl, CH_ThreeSiCl_Three, (CH_Three)_TwoSiCl_Two, (C
H_Three)_ThreeAlkyl-containing chlorosilanes such as SiCl;
CH_Three(CH_Two)₃₀Si (OCH_Three)_Three, CH_Three(CH_Two)₂₀
Si (OCH_Three)_Three, CH_Three(CH_Two)₁₈Si (OCH_Three)_Three,
CH_Three(CH_Two)₁₆Si (OCH_Three)_Three, CH_Three(CH _Two)₁₄
Si (OCH_Three)_Three, CH_Three(CH_Two)₁₂Si (OCH_Three)_Three,
CH_Three(CH_Two)_TenSi (OCH_Three)_Three, CH_Three(CH_Two)₉S
i (OCH_Three)_Three, CH_Three(CH_Two)₈Si (OCH_Three)_Three, C
H_Three(CH_Two)₇Si (OCH_Three)_Three, CH_Three(CH_Two)₆Si
(OCH_Three)_Three, CH_Three(CH_Two)_FiveSi (OCH_Three)_Three, CH
_Three(CH_Two)_FourSi (OCH_Three)_Three, CH_Three(CH_Two)_ThreeSi (O
CH_Three)_Three, CH_Three(CH_Two)_TwoSi (OCH_Three)_Three, CH_ThreeC
H_TwoSi (OCH_Three)_Three, (CH_ThreeCH_Two)_TwoSi (OC
H_Three)_Two, (CH_ThreeCH_Two)_ThreeSiOCH_Three, CH_ThreeSi (OC
H_Three)_Three, (CH_Three)_TwoSi (OCH_Three)_Two, (CH_Three)_ThreeSiO
CH_Three, CH_Three(CH_Two)₃₀Si (OC_TwoH_Five)_Three, CH_Three(C
H_Two)₂₀Si (OC_TwoH_Five)_Three, CH_Three(CH_Two)₁₈Si (OC
_TwoH_Five)_Three, CH_Three(CH_Two)₁₆Si (OC_TwoH_Five)_Three, CH
_Three(CH_Two)₁₄Si (OC_TwoH_Five)_Three, CH_Three(CH_Two)₁₂Si
(OC_TwoH_Five)_Three, CH_Three(CH_Two)_TenSi (OC_TwoH_Five)_Three,
CH_Three(CH_Two)₉Si (OC_TwoH_Five)_Three, CH_Three(CH_Two) ₈S
i (OC_TwoH_Five)_Three, CH_Three(CH_Two)₇Si (OC_TwoH_Five)_Three,
CH_Three(CH_Two)₆Si (OC_TwoH_Five)_Three, CH_Three(CH_Two)_FiveS
i (OC_TwoH_Five)_Three, CH_Three(CH_Two)_FourSi (OC_TwoH_Five)_Three,
CH_Three(CH_Two)_ThreeSi (OC_TwoH_Five)_Three, CH_Three(CH_Two)_TwoS
i (OC_TwoH_Five)_Three, CH_ThreeCH_TwoSi (OC_TwoH_Five)_Three, (CH
_ThreeCH_Two)_TwoSi (OC_TwoH_Five)_Two, (CH_ThreeCH_Two)_ThreeSiOC_Two
H_Five, CH_ThreeSi (OC_TwoH_Five)_Three, (CH_Three)_TwoSi (OC_TwoH
_Five)_Two, (CH_Three)_ThreeSiOC_TwoH_FiveContaining an alkyl group such as
Alkoxysilane; CH_Three(CH_Two)₃₀Si (OCOC
H_Three)_Three, CH_Three(CH_Two)₂₀Si (OCOCH_Three)_Three, CH_Three
(CH_Two)₁₈Si (OCOCH_Three)_Three, CH_Three(CH_Two)₁₆S
i (OCOCH_Three)_Three, CH_Three(CH_Two)₁₄Si (OCOCH
_Three)_Three, CH_Three(CH_Two)₁₂Si (OCOCH_Three)_Three, CH
_Three(CH_Two)_TenSi (OCOCH_Three)_Three, CH_Three(CH_Two)₉S
i (OCOCH_Three)_Three, CH_Three(CH_Two)₈Si (OCOC
H_Three)_Three, CH_Three(CH_Two)₇Si (OCOCH_Three)_Three, CH_Three
(CH_Two)₆Si (OCOCH_Three)_Three, CH_Three(CH_Two)_FiveSi
(OCOCH_Three)_Three, CH_Three(CH_Two)_FourSi (OCOC
H_Three)_Three, CH_Three(CH_Two)_ThreeSi (OCOCH_Three)_Three, CH_Three
(CH_Two)_TwoSi (OCOCH_Three)_Three, CH_ThreeCH_TwoSi (OC
OCH_Three)_Three, (CH_ThreeCH_Two)_TwoSi (OCOCH_Three)_Two,
(CH_ThreeCH_Two)_ThreeSiOCOCH_Three, CH_ThreeSi (OCOC
H_Three)_Three, (CH_Three)_TwoSi (OCOCH_Three)_Two, (CH_Three)_Three
SiOCOCH_Three Acyloxy containing alkyl groups such as
Run; CH_Three(CH_Two)₃₀Si (NCO)_Three, CH_Three(C
H_Two)₂₀Si (NCO)_Three, CH_Three(CH_Two)₁₈Si (NC
O)_Three, CH_Three(CH_Two)₁₆Si (NCO)_Three, CH_Three(CH
_Two)_{1 Four}Si (NCO)_Three, CH_Three(CH_Two)₁₂Si (NCO)
_Three, CH_Three(CH_Two)_TenSi (NCO)_Three, CH_Three(CH_Two)₉
Si (NCO)_Three, CH_Three(CH_Two)₈Si (NCO)_Three, C
H_Three(CH_Two)₇Si (NCO)_Three, CH_Three(CH_Two)₆Si
(NCO)_Three, CH_Three(CH_Two)_FiveSi (NCO)_Three, CH_Three
(CH_Two)_FourSi (NCO)_Three, CH_Three(CH_Two)_ThreeSi (NC
O)_Three, CH_Three(CH_Two)_TwoSi (NCO)_Three, CH_ThreeCH_TwoS
i (NCO)_Three, (CH_ThreeCH_Two)_TwoSi (NCO)_Two, (C
H_ThreeCH_Two)_ThreeSiNCO, CH_ThreeSi (NCO)_Three, (C
H_Three)_TwoSi (NCO)_Two, (CH_Three)_ThreeLike SiNCO
Examples of alkyl group-containing isocyanate silanes
it can.

Further, by treating with a polyalkylene oxide group and an organosilane having a hydrolyzable group in the molecule, the critical inclination 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 (underlying film), the surface of the underlayer 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.

[0048]

Embodiments of the present invention will be described below.

Example 1 Concentrated hydrochloric acid (concentration: 35% by weight) 9
600 g of concentrated sulfuric acid (concentration: 95% by weight) was dropped into 0 g, and the generated hydrogen chloride (HCl) gas was dissolved in 500 g of dehydrated ethanol (manufactured by Kanto Chemical Co., Ltd., water content: 0.005% or less). An HCl ethanol solution containing 8% by weight was prepared. This HCl ethanol solution 31
187.5 g of dehydrated ethanol was added to 2.5 g,
An ethanolic HCl solution containing 3.0% by weight of HCl was obtained. 97.8 g of this 3.0% HCl ethanol solution
And tetraethoxysilane (Shin-Etsu Chemical Co., Ltd.)
0.4 g was further added, and 1.8 g of water was further added, followed by stirring for 30 minutes to obtain a silica film coating composition. 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 Shin-Etsu Chemical Co., Ltd.) is added to ethanol 98
g, and 1.0 g of 0.1N hydrochloric acid was further added.
The mixture was stirred for 1 hour to obtain a water-repellent agent.

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.

Thereafter, 3 ml of the above-mentioned water repellent is applied to the surface of the glass substrate coated with the silica film, and the excess water adhering agent 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 Co., Ltd.), the water-repellent glass was used to determine the weight of the water droplets.
The initial static water droplet contact angle (hereinafter simply referred to as contact angle) was measured as mg. As a friction test, a dry cloth was attached to a reciprocating abrasion tester (manufactured by Shinto Kagaku) and a load of 0.3 kg /
The surface of the water-repellent film was slid back and forth 3000 times under the condition of cm ² ,
Thereafter, 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 unevenness of the film.
The case where there was no film unevenness was indicated as “OK”, and the case where film unevenness occurred was indicated as “NG”. As shown in Table 2, the contact angle of the silica film surface was 29 degrees, and the initial contact angle after the water-repellent treatment was 1
08 °, the contact angle after the friction test was 96 °, and the appearance was good “OK”.

Example 2 Example 1 was repeated except that the addition amount of water was changed to 0.0 g and the addition amount of the 3.0% ethanol solution was changed to 99.6 g in the preparation of the silica membrane treating solution in Example 1.
Water-repellent treated glass was obtained in the same manner as described above. Table 1 shows the composition of the silica film treatment liquid, and Table 2 shows the thickness of the silica film, various contact angles, and the like.

[Examples 3 and 4] In the same manner as in Example 1, a 2.0% HCl ethanol solution was prepared, and a 2.0% HCl ethanol solution was prepared.
2.0 g (Example 3) of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 96.5 g of an ethanol solution of HCl.
Alternatively, 0.05 g (Example 3) was added, and water 1.
5 g was added and stirred for 30 minutes to obtain a coating composition. The contents of tetraethoxysilane (in terms of silica), hydrochloric acid and water in each treatment solution are as shown in Table 1. Thereafter, a water-repellent glass was obtained in the same manner as in Example 1. Table 2 shows the thickness of the silica film of the water-repellent treated glass obtained in Examples 3 and 4, various contact angles, and the like.

[Examples 5 and 6] In the same manner as in Example 1, a 0.3% (Example 5) or 4.5% (Example 6) ethanol solution of HCl was prepared, and a predetermined HC solution was prepared.
99.3 g and 98.6 g of 1 ethanol solution respectively
And tetraethoxysilane (Shin-Etsu Chemical Co., Ltd.)
0.4 g was added, and 0.3 g (Example 5) and 1.0 g (Example 6) of water were further added, followed by stirring for 30 minutes to obtain a coating composition. The contents of tetraethoxysilane (in terms of silica), hydrochloric acid and water in each treatment solution are as shown in Table 1. Thereafter, a water-repellent glass was obtained in the same manner as in Example 1. Table 2 shows Examples 5 and 6.
The thickness, various contact angles, etc. of the silica film of the water-repellent glass obtained in the above section are shown.

Example 7 As in Example 1, 3.0%
A HCl ethanol solution was prepared, and 0.4 g of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 98.6 g of the 3.0% HCl ethanol solution.
0 g was added and stirred for 30 minutes to obtain a coating composition. The contents of tetraethoxysilane (in terms of silica), hydrochloric acid and water in this treatment liquid are as shown in Table 1. Thereafter, a water-repellent glass was obtained in the same manner as in Example 1. Table 2 shows the thickness of the silica film of the water-repellent glass obtained in Example 7, various contact angles, and the like.

Example 8 64.8 g of dehydrated ethanol
9.8 g of acetylacetone, aluminum tri-
25.4 g of sec-butoxide (manufactured by Kanto Chemical Co., Ltd.) was dissolved to obtain a 5% by weight alumina raw material liquid in terms of oxide.

In the same manner as in Example 1, a 3.0% HCl ethanol solution was prepared. To 98.55 g of the 3.0% HCl ethanol solution, 0.12 g of the above alumina raw material solution and tetraethoxysilane (Shin-Etsu Chemical Co., Ltd.) 0.33 g
Was added, and 1.0 g of water was further added, followed by stirring for 30 minutes to obtain a coating composition. The contents of tetraethoxysilane (in terms of silica), hydrochloric acid and water in this treatment liquid are as shown in Table 1. Thereafter, a water-repellent glass was obtained in the same manner as in Example 1. Table 2 shows the thickness of the silica film of the water-repellent glass obtained in Example 7, various contact angles, and the like.

Example 9 78.6 g of dehydrated ethanol
4.1 g of acetylacetone and 17.4 g of zirconium-tetra-n-butoxide (Kanto Chemical) were dissolved in
A zirconia raw material liquid of 5% by weight in terms of oxide was obtained.

In the same manner as in Example 1, a 3.0% HCl ethanol solution was prepared. To 98.6 g of the 3.0% HCl ethanol solution, 0.12 g of the zirconia raw material solution and tetraethoxysilane (Shin-Etsu Chemical Co., Ltd. 0.33 g
Was added, and 1.0 g of water was further added, followed by stirring for 30 minutes to obtain a coating composition. The contents of tetraethoxysilane (in terms of silica), hydrochloric acid and water in this treatment liquid are as shown in Table 1. Thereafter, a water-repellent glass was obtained in the same manner as in Example 1. Table 2 shows the thickness of the silica film of the water-repellent treated glass obtained in Example 8, various contact angles, and the like.

Example 10 The coating composition prepared in Example 1 was placed on a washed soda-lime silicate glass substrate (300 × 300 mm) at a humidity of 30% and at room temperature in the above silica film treating solution. Immersion, pulling speed 600m
It was applied by a dipping method at m / min and dried for about 1 minute, and a silica film having a thickness of about 60 m was coated on the surface of the glass substrate.

Next, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si
1 g of (OCH ₃ ) ₃ (heptadecafluorodecyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to ethanol 98
g, and 1.0 g of 0.1N hydrochloric acid was further added.
The mixture was stirred for 1 hour to obtain a water-repellent agent.

Then, 3 ml of the above water repellent was applied to a cotton cloth on the surface of the glass substrate coated with the silica film, and the excess water repellent was wiped off with a new cotton cloth. A treated glass was obtained. Table 2 shows the thickness of the silica film of the water-repellent glass obtained, various contact angles, and the like.

Example 11 A water-repellent treatment was conducted in the same manner as in Example 1 except that tetraethoxysilane (manufactured by Tokyo Chemical Industry) was used instead of the tetraethoxysilane used for preparing the silica film treating solution in Example 1. A glass was obtained. Table 1 shows the composition of the silica treatment liquid and the thickness of the silica film, various contact angles, and the like.

Example 12 CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC) used for preparing the water-repellent treatment liquid in Example 1
H _{3) 3} (heptadecafluorodecyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., except for changing Ltd.) in n- octadecyl trimethoxysilane, give a water-repellent and low friction glass in the same manner as in Example 1 Was. 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.
Degrees, 92 degrees. In addition, a dry cloth was attached to a wear coefficient measuring instrument (manufactured by Shinto Kagaku), and the friction coefficient between the film surface and the dry cloth was measured to obtain an initial friction coefficient of 0.24 and a friction coefficient of 0.24 after the wear test. Was. Initial friction coefficient of 0.37 when treated with an organosilane having a fluoroalkyl group as in Example 1, initial friction coefficient of untreated ordinary glass 0.4
A glass having a smaller coefficient of friction than that of No. 2 was obtained. The coefficient of friction after the friction test was almost unchanged from that before the friction test (initial stage).

Example 13 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 Shin-Etsu Chemical Co., Ltd.) was replaced with [methoxy (polyethyleneoxy) propyl] trimethoxysilane (manufactured by Chisso Corporation, content: 90%, molecular weight: 460-590, ethylene oxide) A functional film was obtained in the same manner as in Example 1 except that the number of units was changed from 6 to 9), in which the critical inclination angle at which water droplets began to roll was low and dirt was not easily adsorbed or adhered.

The initial contact angle of the above 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, and the critical inclination angle after the friction test was 4 degrees, and almost the same performance as the contact angle and the critical inclination angle before the friction test was maintained.

Comparative Example 1 Ethanol (water content: approx.
A hydrolyzate (average molecular weight: 4) of ethyl silicate (average degree of polymerization: about 5) was added to 96 g of 35% by weight (manufactured by Nacalai Tesque).
08.5, “HAS-10”, 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 solution was flow-coated on a washed glass substrate (300 × 300 mm) at a humidity of 30% and at room temperature, and was applied.
Dried in minutes. Thereafter, the substrate was fired at 600 ° C. for 1 hour to obtain a silica film. The hardness of the silica film before baking was measured by pencil hardness. As a result, the film was scratched when the film was scratched with the pencil “B”. And the silica film after the above calcination is
The membrane was not damaged even when the membrane was scratched with the pencil of the "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.

[Comparative Example 2] Ethanol (water content about 0.
35 wt%, 99.1 g of Nacalai Tesque), 0.4 g of tetraethoxysilane (Shin-Etsu Chemical Co., Ltd.),
0.5 g of 0.1 N hydrochloric acid 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
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.

Comparative Example 3 In the preparation of the silica membrane treating solution in Example 1, the amount of tetraethoxysilane added was 0.4
g instead of 15.0 g, and the amount of dehydrated ethanol added was 9
Example 1 except that 83.0 g was used instead of 7.8 g.
Water-repellent treated glass was obtained in the same manner as described above. Table 1 shows the composition of the silica film treatment liquid, and Table 2 shows the thickness of the silica film, various contact angles, and the like.

Comparative Example 4 Concentrated hydrochloric acid (concentration: 35% by weight) 9
600 g of concentrated sulfuric acid (concentration 95% by weight) was dropped into 0 g, and the generated hydrogen chloride (HCl) gas was dissolved in 80 g of dehydrated ethanol (manufactured by Kanto Chemical Co., Ltd., water content 0.005% or less). An HCl ethanol solution containing 1% by weight was prepared. This HCl ethanol solution 39
101.6 g of dehydrated ethanol was further added to 8.4 g,
An HCl ethanol solution containing 20.0% by weight of HCl was obtained. This 20.0% HCl ethanol solution 98.6
g to tetraethoxysilane (Shin-Etsu Chemical Co., Ltd.)
0.4 g was added, and 1.0 g of water was further added, followed by stirring for 30 minutes to obtain a coating composition. The contents of tetraethoxysilane (in terms of silica), hydrochloric acid and water in this treatment liquid are as shown in Table 1. Thereafter, a water-repellent glass was obtained in the same manner as in Example 1. Table 2 shows the thickness of the silica film of the water-repellent glass obtained, various contact angles, and the like.

Comparative Example 5 The amount of water added (1.8 in the preparation of the composition for coating a silica film in Example 1)
g) was changed to 6.0 g, and the amount of the 3.0% ethanol solution (97.8 g) was changed to 93.6 g, to obtain a water-repellent treated glass in the same manner as in Example 1. Table 1 shows the composition of the silica film treatment liquid, and Table 2 shows the thickness of the silica film, various contact angles, and the like.

Comparative Example 6 A water-repellent and low friction resistance glass was obtained in the same manner as in Example 12, except that the silica film coating step of Example 12 was not performed. The initial contact angle after the water-repellent treatment was 95 degrees, which was equal to the value for the glass of Example 12, but the contact angle after the friction test was 55 degrees, which was a value (92 degrees) for the glass of Example 12. The film was remarkably low in comparison with the film and had poor wear 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 7 A water-repellent and low frictional resistance glass glass was obtained in the same manner as in Example 13 except that the silica film coating step in Example 13 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 13. However, the contact angle after the friction test was 22 degrees, and the critical inclination angle was 25 degrees. The contact angle was significantly reduced and the critical inclination angle was significantly increased, and the wear resistance was poor.

[0080]

[Table 1] ト リ Aluminum trisilconium tetraalkoxysilane phthaloxide tetra pentoxide hydrochloric acid water (SiO ₂ equivalent) (Al ₂ O ₃ conversion) (ZrO ₂ conversion) (% by weight) (wt%) (wt%) (defined) (wt%) ───────────────── ─────────────── Example 1 0.12 0 0 0.64 1.8 Example 2 0.12 0 0 0.64 0.0 Example 3 0.58 0 0 0.43 1.5 Example 4 0.014 0 0 0.43 1.5 Example 5 0.12 0 0 0.064 0.3 Example 6 0.12 0 0 0.96 1.0 Example 7 0.12 0 0 0.64 1.0 Example 8 0.095 0.006 0 0.64 1.0 Example 9 0.095 0 0.006 0.64 1.0 Example 10 0.12 0 0 0.64 1.8 Example 11 0.16 0 0 0.64 1.8 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Comparative Example 1 0.12 0 0 0.00003 0.65 Comparative Example 2 0.12 0 0 0.0004 0.85 Comparative Example 3 4.34 0 0 0.64 1.8 Comparative Example 4 0.12 0 0 4.30 1.0 Comparative Example 5 0.12 0 0 0.64 6.0 ────────────────────────────────

[0081]

[Table 2] ───────────────────────── Silica-based water-repellent glass ────── ────────膜厚 Film thickness Contact angle Initial after friction test Appearance Contact angle Contact angle (nm) (degree) (degree) (degree) ────────────────────例 Example 1 40 29 108 96 OK Example 2 40 31 109 101 OK Example 3 100 27 107 97 OK Example 4 15 29 107 94 OK Example 5 40 30 109 96 OK Example 6 40 31 108 94 OK Example 7 40 28 109 104 OK Example 8 40 27 108 105 OK Example 9 35 28 107 102 OK Example 10 60 34 108 104 OK Example 11 40 31 107 99 OK −−−−−−−− −−−−−−−−−−−−−−−−−−− Comparative Example 1 40 2 106 50 NG Comparative Example 2 45 24 110 70 OK Comparative Example 3 300 32 110 64 NG Comparative Example 4 40 30 109 72 NG Comparative Example 5 40 28 109 82 OK ─────────────────────────

[0082]

As described above, according to the present invention, an article coated with a dense and strong silica film can be produced in a short time without the need for a treatment such as sintering which leads to an increase in production cost. And easily manufactured. 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 Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C03C 17/30 C03C 17/30 A C04B 41/82 C04B 41/82 A C09J 183/04 C09J 183/04 ( 72) Inventor Kazutaka Kamiya 3-5-1, Doshu-cho, Chuo-ku, Osaka-shi, Japan In-house Glass Co., Ltd. (72) Inventor Toyoyuki Teranishi 3-5-1, Doshu-cho, Chuo-ku, Osaka-shi, Japan In-house Glass Co., Ltd. (72) Inventor Mitsuo Asai 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture F-term (reference) 4D075 BB24Z CA09 CA36 DA06 DB13 EA05 EB42 EB56 EC07 EC30 4G059 AA01 AB09 AC22 AC24 EA01 EA05 EB07 FA05 FA22 FB05 GA01 GA12 4G072 AA35 AA36 AA41 BB09 EE05 EE06 EE07 FF01 FF02 FF07 GG03 HH30 JJ38 JJ39 JJ46 JJ47 KK17 LL15 MM0 2 PP17 RR12 TT30 UU30 4J040 AA011 HA086 HA126 HA166 HA301 HB07 HB09 HD32 HD41 KA23 LA07 MA05

Claims (25)

[Claims] 1. A method for producing a silica-based film-coated article in which a coating liquid containing a silicon alkoxide and an acid in an alcohol solvent is applied to a substrate, wherein the coating liquid comprises the acid and water in a weight ratio of acid / water. Is 0.58
A method for producing a silica-based membrane-coated article, wherein the article is contained as described above, and wherein the acid is obtained by dissolving hydrogen halide in the alcohol solvent. 2. The coating liquid comprises: (A) at least one of silicon alkoxide and its hydrolyzate (including partial hydrolyzate) 0.010 to 3% by weight (in terms of silica); The method for producing a silica-based membrane-coated article according to claim 1, comprising 0.0010 to 3.0N, and (C) 0 to 10% by weight of water. 3. The method according to claim 1, wherein the hydrogen halide is hydrogen chloride. 4. The coating liquid comprises: (A) at least one of silicon alkoxide and its hydrolyzate (including partial hydrolyzate) in terms of silica;
The silica according to any one of claims 1 to 3, wherein the silica (B) and the acid (B) are contained such that “(B) component (prescribed) / (A) component (% by weight)” is 0.010 or more. A method for producing a system-coated article. 5. The coating liquid contains the (B) acid and (C) water such 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 any one of claims 1 to 4. 6. The coating liquid comprises: (A) at least one of silicon alkoxide and a hydrolyzate thereof (including a partial hydrolyzate) 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 5, comprising: (0) an acid of 0.010 to 1.5N, and (C) water of 0 to 2% by weight. 7. The method according to claim 1, wherein the silicon alkoxide of the component (A) is tetramethoxysilane or tetraethoxysilane. 8. 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 the substituted silica-based film-coated article according to any one of claims 1 to 7. 9. The method according to claim 8, wherein the β-diketone of the ligand is acetylacetone. 10. The method for producing a silica-based film-coated article according to claim 8, wherein the metal alkoxide is an alkoxide of aluminum or zirconium. 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 substrate according to claim 1, wherein the substrate is a glass plate.
13. The method for producing a silica-based film-coated article according to any one of the above items 12. 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. 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 further comprising applying the functional film composition. 16. 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 15. 17. The method according to claim 16, wherein the hydrolyzable functional group is an alkoxyl group. 18. The method for producing a functional film-coated article according to claim 15, wherein the composition for a functional film is a composition for forming a water-repellent film. 19. The composition for forming a water-repellent film contains 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 19. A method for producing the functional film-coated article according to Item 18. 20. The method for producing a functional film-coated article according to claim 15, wherein the composition for a functional film is a composition for forming a water-repellent and low friction resistance film. 21. 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
A method for producing the functional film-coated article according to Item 0. 22. The method for producing a functional film-coated article according to claim 15, wherein the composition for a functional film is a film-forming composition having excellent rolling properties of water droplets and having antifouling properties. 23. The film-forming composition which has excellent rolling properties of water droplets and has antifouling properties, comprises an organosilane containing an alkoxyl group and a polyalkylene oxide group in a molecule and a hydrolyzate thereof (partial hydrolysis). 23. The method for producing a functional film-coated article according to claim 22, which comprises at least one of the above. 24. A functional film-coated article obtained by the method according to any one of claims 15 to 23. 25. (A) at least one of silicon alkoxide and its hydrolyzate (including partial hydrolyzate) 0.010 to 3% by weight (in terms of silica); (B) hydrohalic acid; (C) 0 to 10% by weight of water, wherein the weight ratio of the component (B) / water is 0.58 or more, and (D) a liquid for coating a silica-based film comprising the remainder of alcohol. Composition.