JPH09194238A - Water-repellent oxide film and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily and efficiently obtain a water-repellent oxide film not deteriorating optical characteristics, considerably improving light and wear resistances as well as water repellency, excellent in adhesion, durability, weather resistance, etc., and useful as a window material for construction or for an automobile, etc., by a simple film forming means at a low cost. SOLUTION: A coating liq. A contg. tetraisocyanatosilane which cures at ordinary temp. as the principal component is applied on a glass substrate, dried at ordinary temp. and heat-treated to form a silica base film. A coating liq. B made of an alkoxysilane type water repellent having one or more side chains each having a fluorocarbon group is applied on the silica base film to form a water-repellent film. The objective water-repellent oxide film made of a laminated film consisting of the silica base film and the water-repellent film is produced.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention can be obtained more simply and efficiently, exhibits excellent water repellency, and also has markedly improved light resistance and abrasion resistance, weather resistance, chemical resistance, etc. Regarding a water-repellent oxide film having excellent durability and a method for producing the same, it is particularly useful for window glass and mirrors for construction, vehicle, ship, aircraft, etc., and various articles for construction and construction, etc. Provided is a water-repellent oxide film that can be widely used in the above and a manufacturing method thereof.

[0002]

2. Description of the Related Art Recently, as a water-repellent film such as water-repellent glass,
Attempts have been made to use an isocyanate silane compound as a single layer on the glass surface or as an upper layer of two layers.

For example, Japanese Patent Publication No. 25990/1990 discloses a method for forming a silicon oxide coating, which comprises treating the surface of a substrate with a silane isocyanate compound containing a Si-NCO bond in the molecule. Is described. Among them, the silane isocyanate compound has the formula Si (NCO) ₄ , R _n Si
(NCO) _4-n , (RO) _n Si- (NCO) _4-n (wherein R is a hydrocarbon group with or without a substituent, n = 1, 2 or 3), or a compound thereof Condensates of compounds, and compounds containing two or more NCO groups directly bonded to Si, which are condensed with silicic anhydride or a polysiloxane compound and the compound of the above formula, are mentioned.

Further, for example, in Japanese Patent Application Laid-Open No. 60-219234,
A method for making a composite membrane is described, which includes (1) Acting on a substrate.
From rilpolyol and polyfunctional organic isocyanate compounds
The primer composition is
OH has an OH value of 10 or more and 200 or less. NCO / OH ratio is 0.6
 And (2) heating the primer composition and
And / or cure by drying, (3) the curing plastic
General formula R on the imager layer¹ _aR^Two _bSi (OR^Three)_4-abRepresented by
Coating comprising an organosilicon compound and its hydrolyzate
Coating composition to cure (where R¹, R^TwoAre each
A kill group, an alkenyl group, an allyl group, or a halogen group,
Epoxy group, amino group, mercapto group, methacryloxy group
Hydrocarbon group having a Si group or a cyano group, R^ThreeIs the carbon number
Is an alkyl group of 1 to 8, an alkoxyalkyl group, an acyl
A phenyl group, a and b are 0 or 1
Is described.

Further, for example, Japanese Unexamined Patent Publication (Kokai) No. 4-342443 describes an article for construction and construction, which comprises a base material having at least two surface-treated layers, or has the base material as a constituent element. In the building / building article, the first layer, which is the outermost layer of the surface treatment layer, is a layer obtained by treating with the isocyanate silane compound (I), and the second layer, which is the lower layer in contact with the outermost layer, is hydrolyzed. It is described that it is a layer obtained by treating with a decomposable silane compound (II) or a partial hydrolysis product thereof.

[0006] In addition, for example, in "1994, 102 [2] 206-209, The Ceramic Society of Japan,""Abrasion resistance controlling factor of water-repellent treated glass" is described, and tetraisocyanate silane is used as a raw material at room temperature. Ting (about 100n
m) followed by a water repellent treatment with a solution of fluoroalkyl isocyanate cyanate [C ₉ F ₁₉ C ₂ H ₄ Si (NCO) ₃ ].

Further, for example, Japanese Patent Application Laid-Open No. 6-184527 filed by the present applicant describes a water repellent treatment agent, a water repellent treatment base material and a method for producing the same, and describes fluoroalkylsilane compounds, long chain aliphatic silanes. Compound and Silicon Isocyanate
In a water repellent agent comprising a mixed solution of at least two kinds of compounds and a dilute solution and an acid catalyst, the fluoroalkylsilane compound is 0 to 5 parts by weight and the compound is 0 to 15 parts by weight. One or two of the long-chain aliphatic silane compounds are selected and used, after diluting with 90 to 110 parts of a diluting solvent, 0.1 to 5 parts of an acid catalyst is added, and then 0 to
A water repellent treatment agent prepared by adding 10 parts of a silicon isocyanate compound. Water-repellent treated glass with a film with a thickness of 30 nm or less with the treatment agent. And its manufacturing method are described.

[0008]

As described above, for example, in the method for forming a silicon oxide coating disclosed in Japanese Patent Publication No. 25990/1990, the glass surface is coated with silicon oxide in an atmosphere at room temperature (room temperature). Although there is a description that it is possible, there is no description about the underlayer film, particularly about the underlayer film of the water repellent oxide film.

Further, for example, in the method for producing a composite film described in JP-A-60-219234, the composite film is made into two layers, and the composite film is coated with a metal, an inorganic oxide or the like to have a heat ray reflecting function or the like. Although it is described that the base film is formed, the surface activity of the base film is not sufficient, and it is difficult to say that the base film has sufficient heat resistance.

Further, for example, in the article for construction and construction described in Japanese Patent Laid-Open No. 4-342443, silane having a functional group that cures at room temperature, such as tetrachlorosilane, is explosive and cannot be used easily. Further, since other functional groups do not cure at room temperature, the hardness of the film is poor, and heat treatment at a high temperature is necessary (in practice) to obtain film strength. Further, with the isocyanate silane-based water repellent, the reaction is not mild because the stimulants such as ammonia and isocyanic acid (HNCO) are generated during the reaction, and the application is difficult.

Further, for example, the Japan Ceramic Society Journal,
1994, 102 [2] 206-209, "Abrasion resistance controlling factor of water-repellent glass", at room temperature coating (about 100 nm) using tetraisocyanate silane as a raw material, and then fluoroalkyl isocyanate. Tosilane (C ₉ F ₁₉ C ₂ H
_{In the} water repellent treatment method using a solution of ₄ Si (NCO) ₃ ], the reaction is not mild because stimulants such as ammonia and isocyanic acid (HNCO) are generated during the reaction by the isocyanate-silane water repellent, It has a surface that is difficult to apply.

Furthermore, for example, the water repellent treatment agent, the water repellent treated base material and the manufacturing method thereof described in Japanese Patent Application Laid-Open No. 6-184527, which the present applicant has already filed, are excellent in the contact angle of water droplets and the falling angle of water droplets. However, due to the fact that it is a one-layer film, it tends to show variations in the adhesion between the film and the glass over time, which means that it is more durable over the long term from recent severe needs. From the above, it is desired to further stabilize and enhance the adhesion between the film and the glass, and to provide a stable and more durable light resistance.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above conventional problems, and a hard silica film is formed on a glass substrate by drying at room temperature (room temperature) and heat treatment. In addition, a specified water repellent agent that exhibits a more water-repellent performance that is safe, stable, stable, and easy to apply is applied in a good working environment on the surface-active silica film. In addition to having excellent water repellency by firing as a heat treatment, it also significantly improves light resistance and abrasion resistance, and various physical properties such as chemical resistance and durability. A water-repellent oxide film that improves the above performance can be efficiently obtained with simple equipment and a simple method without impairing the optical properties. Window materials, glass products with various films, various It is to provide useful water-repellent oxide film and its production method in instrumentation building materials Hinto.

That is, according to the present invention, a silica base film formed by coating a glass substrate with a coating liquid A containing tetraisocyanate silane as a main component which cures at room temperature, drying it at room temperature, and subjecting it to heat treatment. A two-layer laminated film comprising a water-repellent film obtained by applying a coating liquid B made of an alkoxysilane-based water repellent having one or more side chains having a fluorocarbon group on the silica-based film to give a water-repellent treatment. A water-repellent oxide film comprising:

In addition, the coating solution B comprising an alkoxysilane water repellent having at least one side chain having a fluorocarbon group is an alkoxysilane compound having at least one side chain having a fluorocarbon group, or The water-repellent oxide film as described above, which is a coating liquid containing at least one of a mixture of an alkoxysilane compound having at least one side chain having a fluorocarbon group and a long-chain aliphatic silane compound.

Further, a coating solution B comprising an alkoxysilane-based water repellent having at least one side chain having a fluorocarbon group is (C _n F _{2n + 1} C ₂ H ₄ ) _a SiR ¹ _b (OR ² ) _4-ab [wherein R ¹ and R ² are alkyl groups, and n is an integer of 1 or more. a = 1,2,3.
b = 0,1,2. a + b = 1,2,3. ] The water-repellent oxide film as described above, which is a coating liquid containing an alkoxysilane having one or more side chains having a fluorocarbon group as a main component.

Further, a coating solution A containing tetraisocyanate silane as a main component which cures at room temperature is applied onto a glass substrate, dried at room temperature, and heat-treated at 700 ° C. or lower for 0.1 minute or more to obtain a silica base. After forming a film, the silica base
A coating solution B made of an alkoxysilane-based water repellent having at least one side chain having a fluorocarbon group is applied onto the base film to make it water repellent, and a silica base film and a water repellent film are formed. A method for producing a water-repellent oxide film, comprising forming a water-repellent oxide film formed of a laminated film.

Further, the coating solution A comprises tetraisocyanate silane and a diluting solvent, and the mixing ratio thereof is a weight ratio of tetraisocyanate silane: diluting solvent = 1: 4.
To 1: 999. The method for producing a water-repellent oxide film as described above, characterized in that

Further, the above-mentioned water-repellent oxide film is characterized in that the heat treatment after coating the coating solution A and drying at room temperature is from 50 ° C. to 670 ° C. for 0.1 minutes to 24 hours. Manufacturing method.

Further, the solid content concentration of the coating liquid B consisting of the alkoxysilane water repellent having at least one side chain having a fluorocarbon group is 0.1 to 5% by weight in terms of oxide, and the viscosity is The method for producing a water-repellent oxide film as described above, which is 0.2 to 7 cP.

Furthermore, the coating solution B comprising an alkoxysilane water repellent having one or more side chains having a fluorocarbon group is an alkoxysilane compound having one or more side chains having a fluorocarbon group, Or a coating solution containing at least one of a mixture of an alkoxysilane compound having at least one side chain having a fluorocarbon group and a long-chain aliphatic silane compound, the side chain having a fluorocarbon group in a weight ratio. 0.1 to 5 parts of an alkoxysilane compound having one or more of the above, 0 to 15 parts of a long-chain aliphatic silane compound, and 90 to 110 parts of a dilute solution, to which 0.1 to 5 parts of an acid catalyst is added, and further silicon isocyanate is added. The method for producing a water-repellent oxide film as described above, characterized in that the solution is a solution to which 0 to 10 parts of a compound is appropriately added and has a viscosity of 0.5 to 6 cP.

Furthermore, a coating solution B composed of an alkoxysilane water repellent having one or more side chains having a fluorocarbon group is (C _n F _{2n + 1} C ₂ H ₄ ) _a SiR ¹ _b ( OR ² )
_4-ab [wherein R ¹ and R ² are alkyl groups, and n is an integer of 1 or more.
a = 1,2,3. b = 0,1,2. a + b = 1,2,3. ] The method for producing a water-repellent oxide film as described above, which is a coating liquid containing, as a main component, an alkoxysilane having at least one side chain having a fluorocarbon group.

The method for producing a water-repellent oxide film as described above, characterized in that the heat treatment after applying the coating liquid B in the water repellent treatment is at room temperature to 400 ° C. for 0.1 minute or more.
Further, the heat treatment after applying the coating liquid B according to claim 7 is carried out at 100 ° C. to 400 ° C. for 0.1 minutes to 120 minutes, wherein the water repellent oxide film is produced.

Further, the heat treatment after applying the coating solution B according to claim 8 is carried out at room temperature to 160 ° C. for 10 minutes or longer, and at room temperature for 12 hours or longer. For producing a water-repellent oxide film.

The coating method of the coating liquids A and B is as follows.
The above-mentioned water-repellent oxide film manufacturing methods are provided, each of which is hand-painting or existing coating means.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Here, as described above, a coating solution A containing tetraisocyanate silane as a main component which cures at room temperature is applied onto a glass substrate, dried at room temperature, and heat-treated to form. The applied silica base film can be applied by a wide range of coating methods from hand coating to existing coating methods such as spin coating, is dried at room temperature such as room temperature, and is heat treated at 700 ° C or lower for 0.1 minute or more. Since it is possible to promote the reaction to form a harder film, and to appropriately select the film thickness from a thin molecular film, for example, because it can be efficiently obtained with existing equipment and a simple method, Further, the surface of the film becomes more active by heat treatment, and for example, the adhesion to the water-repellent film on the upper side and the glass surface on the lower side can be made stronger, and the light resistance and abrasion resistance are improved. Equality that contributes significantly to Performance to exert Shirikabe - is because the scan film (underlying layer film).

Further, a coating film to be laminated as a second layer on the silica base film is coated with a coating liquid B made of an alkoxysilane water repellent having at least one side chain having a fluorocarbon group. The water-repellent film which has been subjected to the water-repellent treatment is obtained by using an alkoxysilane-based water-repellent agent having one or more side chains having a fluorocarbon group as the water-repellent agent. It is a mild reaction, easy to apply and easy to obtain a uniform film, and no stimulants such as ammonia and isocyanic acid (HNCO) are generated during the reaction (film formation), and it is necessary in the final step. The heat treatment as a water-repellent treatment can improve the adhesion between the water-repellent film, the base film and the glass, and the complicated work can be performed with simple equipment without the need for large-scale equipment. Deposition by a simple coating method without accompanying This is because the water repellent performance can be sufficiently exhibited, and particularly, the light resistance and the wear resistance can be remarkably improved to bring about a sufficiently excellent practical effect.

The coating solution A comprises tetraisocyanate silane [Si (NCO) ₄ ] and a diluting solvent [eg butyl acetate], and the mixing ratio thereof is a weight ratio of tetraisocyanate silane: diluted. The solvent is preferably 1: 4 to 1: 999, more preferably tetraisocyanate silane: diluting solvent = 1: 9 to 1: 499, and the ratio of these is the coating method or the film thickness and the target product. According to the manufacturing conditions, etc., it is appropriately selected and the optimum ratio is adopted.

Further, the heat treatment after coating the coating solution A and drying at room temperature is performed at 700 ° C. or lower for 0.1 minute or longer, preferably 50 ° C. or higher and 670 ° C. or lower for 0.1 minute or longer and 24 hours or shorter, and more preferably. About 0.1 ° C above 100 ° C and above 550 ° C
It is about 1 minute or more and 2 hours or less, and it is also possible to perform firing at the same time, for example, during the heating bending treatment and / or the strengthening treatment. Further, it is preferable that the heat treatment after applying the coating liquid B in the water repellent treatment is performed at room temperature to about 400 ° C. for about 0.1 minute or more.

Further, the coating solution B comprising an alkoxysilane water repellent having one or more side chains having a fluorocarbon group is an alkoxysilane compound having one or more side chains having a fluorocarbon group, or A water-repellent film is preferably a coating liquid containing at least either a mixture of an alkoxysilane compound having one or more side chains having a fluorocarbon group and a long-chain aliphatic silane compound.

Among them, (C _n F _{2n + 1} C ₂ H ₄ ) _a SiR ¹ _b (OR
² ) _4-ab [wherein R ¹ and R ² are alkyl groups, and n is an integer of 1 or more. a = 1,2,3. b = 0,1,2. a + b = 1,2,3. ] It is more preferable that the coating liquid B is composed mainly of an alkoxysilane having one or more side chains having a fluorocarbon group represented by the following formula.

More specifically, the solid content concentration in the coating liquid B comprising an alkoxysilane water repellent having at least one side chain having the fluorocarbon group is 0.1 to 5% by weight in terms of oxide. And the viscosity is 0.2 to 7 cP, or the weight ratio of the alkoxysilane compound having at least one side chain having a fluorocarbon group is 0.1.
To 5 parts, a long-chain aliphatic silane compound 0 to 15 parts, and a dilute solution 90 to 110 parts in a mixed solution of 0.1 to 5 acid catalyst.
Part is added, and a silicon isocyanate compound 0 to 10 is further added.
The coating solution B has a viscosity of 0.5 to 6 cP.

Further, the heat treatment after applying the coating liquid B in the water repellent treatment is at room temperature to 400 ° C. for 0.1 minutes or more, and, for example, the solid content concentration is 0.1 to 5% by weight in terms of oxide. And the heat treatment after coating the coating liquid B (claim 6) having a viscosity of 0.2 to 7 cP is about 100 to 400 ° C. for about 120 minutes to 1 minute. And an alkoxysilane compound having at least one side chain having a fluorocarbon group is
0.1 to 5 parts of a long-chain aliphatic silane compound, 90 to 110 parts of a dilute solution, and 0.1 to 5 parts of an acid catalyst are added to a mixed solution of 0.1 to 5 parts, and 0 to 10 parts of a silicon isocyanate compound are appropriately added. In the case of heat treatment after applying the coating liquid B (claim 7) having a viscosity of 0.5 to 6 cP, the temperature is from room temperature to about 160 ° C. for about 10 minutes or more, and at room temperature. Is preferably about 12 hours or more.

Furthermore, as a method for applying a film to a glass substrate, hand coating, spin coating, dipping, spraying, flow coating, reverse coating,
Known coating means such as a flexographic method or a printing method, and a coating means combining these can be appropriately adopted.

Furthermore, the fluorocarbon group is included.
As an alkoxysilane compound having one or more side chains
For example, CF_Three(CH_Two)_TwoSi (OCH_Three)_Three, CF_Three(CH_Two)_TwoSiCl_Three, CF
_Three(CF _Two)_Five(CH_Two)_TwoSi (OCH_Three)_Three, CF_Three(CF_Two)_Five(CH_Two)_TwoSiCl_Three, CF
_Three(CF_Two)₇(CH_Two)_TwoSi (OCH_Three)_Three, CF_Three(CF_Two)₇(CH_Two)_TwoSiCl_Three, CF
_Three(CF_Two)₇(CH_Two)_TwoSiCH_ThreeCl_Two, CF_Three(CF_Two)₇(CH_Two)_TwoSiCH_Three(OCH_Three)
_TwoAnd the like.

Furthermore, examples of the long-chain aliphatic silane compound include CH ₃ (CH ₂ ) ₅ Si (OCH ₃ ) ₃ and CH ₃ (CH ₂ ) ₅ SiCl ₃
And the like. Furthermore, the above-mentioned silicon isocyanate
Examples of the compound include (CH ₃ ) ₃ SiNCO, (CH ₃ ) ₂ Si (NCO)
₂ , CH ₃ Si (NCO) ₃ , CH ₂ = CHSi (NCO) ₃ , phenyl-Si (NCO) ₃
, Si (NCO) ₄ , C ₂ H ₅ OSi (NCO) _{3 and the} like.

Furthermore, examples of the diluent solvent include esters such as butyl acetate and ethyl acetate, and ethanol.
, Lower alcohols such as propanol and butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cellosolves such as methyl cellosolve and ethyl cellosolve, aromatic hydrocarbons such as toluene and xylene, Aliphatic hydrocarbons such as n-butane and n-hexane are listed.

Furthermore, examples of the acid catalyst include inorganic acids such as nitric acid, hydrochloric acid and sulfuric acid, dicarboxylic acids such as oxalic acid and hexafluoroglutaric acid, and organic acids such as P-toluenesulfonic acid and trifluoroacetic acid. Can be mentioned.

Furthermore, the glass substrate is an inorganic transparent plate glass, which is colorless or green type,
It is not particularly limited to bronze-based coloring, and its type or color tone, various functionalities, shapes, etc., and it can be used not only as bent plate glass but also as various tempered glass, strength-up glass, flat plate or single plate. ,
It goes without saying that it can also be used as a double-glazing or laminated glass. Needless to say, it may be used in combination with other functional films, and may be used as an organic transparent plate glass such as a PC plate.

As described above, according to the present invention, a silica base formed by applying a coating solution containing tetraisocyanate silane as a main component which cures at room temperature onto a glass substrate, drying at room temperature, and subjecting to heat treatment. And a water-repellent film obtained by applying a coating solution of an alkoxysilane-based water repellent having one or more side chains having a fluorocarbon group on the silica-based film to make the film water-repellent. By the water-repellent oxide film formed of a laminated film and the manufacturing method thereof, the above-mentioned specific underlayer film and specific water-repellent film are combined to be divided into two layers of a base film and a water-repellent film,
Drying at room temperature and adequately calcining, in particular, by heat-treating the base film so that it can be calcined at a higher temperature if necessary, provides a firm adhesion to the water-repellent film and the glass while obtaining a harder underlayer film. It can be made into a thin film, and not only water repellency but also light resistance and abrasion resistance are greatly improved, and it has further superior light resistance, abrasion resistance, weather resistance, durability, and is transparent and has high hardness. In addition, the water-repellent performance can be sufficiently satisfied for a long period of time, and the optical characteristics can be sufficiently satisfied. As a general rule, it is possible to use existing equipment to achieve high safety and no troublesome process. Thus, it is possible to efficiently provide a high-quality water-repellent oxide film.

[0041]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

Example 1 A clear float glass substrate having a size of about 100 mm × 100 mm and a thickness of about 2 mm was sequentially washed with a neutral detergent, water rinse, alcohol, dried and then wiped with acetone to form a glass substrate for coating. .

Tetraisocyanatosilane [Si (NCO) ₄ ,
Matsumoto Seiyaku Co., Ltd.] and butyl acetate [CH ₃ COOC ₄ H ₉ ] are used to obtain two weight ratios of Si (NCO) ₄ : CH ₃ COOC ₄ H ₉ = 1: 49 and 1:74. Two coating solutions A were prepared by mixing.

Next, the coating solution A is applied to the surface of the glass substrate for coating by hand coating with cotton and dried at room temperature for about 5 hours, and then at about 100 ° C. for about 1 hour, about 200 hours.
C. for about 10 minutes, about 200.degree. C. for about 1 hour, about 300.degree. C. for about 10 minutes, spin coating, and after drying in the same manner as above, about 640.degree. C. for about 5 minutes and about 740.degree. C. for about 5 minutes. Each was heat-treated for 4 minutes to form an underlayer film (silica base film) made of a silica film with a film thickness of about 20 nm. [Abrasion resistance test of base layer film] Taber abrasion test: CS-10F Evaluation was made by the difference [ΔH (%) value] in haze value [cloudiness value] before and after 20 rotations.

As a result, about 100 after hand-painting and drying at room temperature
In the case of heat treatment at ℃ for about 1 hour, ΔH value is about 0.5% when the ratio of the coating solution A is 1:49, and ΔH value is 1:74 when the ratio is 1:74.
The H value was about 0.4%.

When heat-treated at about 200 ° C. for about 1 hour after being hand-painted and dried at room temperature, the ratio of the coating solution A is 1:49.
In the case of, the ΔH value is about 0.5%, and in the case of 1:74, the ΔH value is
It was about 0.4%.

Therefore, the silica underlayer film obtained by performing the heat treatment after drying at room temperature had an improved ΔH value of 0.5% or less and improved film hardness. Even when the mixing ratio was 1:24, 1:99, 1: 199, etc., the silica underlayer film was a hard film having a ΔH value of 0.5% or less, and the film hardness was improved.

Then, heptadecafluorodecyltrimethoxysilane [CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , manufactured by Toshiba Silicon KK] and ethanol [C ₂ H ₅ OH] and oxalic acid [HO
OCCOOH ・ 2H ₂ O] in a weight ratio of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si
(OCH ₃ ) ₃ : C ₂ H ₅ OH: HOOCCOOH.2H ₂ O = 1: 100: 2 to obtain a mixed solution, and then to the mixed solution, methyltriisocyanatesilane [CH ₃ Si (NCO) ₃ , manufactured by Matsumoto Pharmaceutical Co., Ltd.] and ethyl acetate [CH ₃ COOC ₂ H ₅ ] in a weight ratio of CH ₃ Si (NCO) ₃ : CH ₃ COOC ₂ H ₅ = 1: 9 The mixed solution was added to prepare a coating solution B.

Next, a few drops of the coating solution B were dropped on the underlayer film and spread evenly using cotton, and this was repeated twice, and then dried at room temperature for about 24 hours to give a film thickness of about
A water repellent film having a thickness of about 20 nm was formed.

In this way, a water-repellent oxide film on the water-repellent treated glass substrate was obtained. The following tests were performed on the obtained glass substrate with a water-repellent oxide film. [Water repellency test] The contact angle with respect to a water drop in the atmosphere (about 25 ° C) was measured using a Kyowa Interface Science CA-A type. [Light resistance test] Super UV (S-UV) Light resistance acceleration test: Irradiation intensity of about 75 mW / cm
² , temperature is about 35 ℃, humidity is about 20% RH. It was evaluated by the relationship between the S-UV irradiation time (hr) and the change in contact angle (°) with time. Super UV
Light fastness tester [Iwasaki Electric Co., Ltd., SUV-W11 type].

The results show that S-UV irradiation time / hr and contact angle /
Fig. 1 shows the relationship of changes with time in ° when the underlayer film is at 100 ° C for 1 hour and is marked with ▲, and when the underlayer film is at 200 ° C for 10 minutes, is marked with ▼ and the underlayer film is at 200 ° C. 1 hour for 1 hour, and ◆ for the underlayer film for 10 minutes at 300 ° C, the initial contact angle is about 110 °, and the S-UV irradiation time is about 1000. Although about 55 °, which is about the same as the one formed by applying the water-repellent agent directly to the glass surface in about a time (hr) (circle mark), the present invention of this example is subjected to S-UV irradiation. The change with time of the contact angle (°) with respect to time is gradual, in particular, the higher the heat treatment temperature is, the more gradual the decrease, and the higher the heat treatment temperature is, the more the light resistance is improved.
It had the desired performance.

Example 2 An underlayer film similar to that in Example 1 was formed on the same glass substrate as in Example 1. When evaluated in the same manner as in Example 1,
It was a hard film similar to that in Example 1.

Then, heptadecaful as in Example 1
Orodecyltrimethoxysilane [CF _Three(CF_Two)₇(CH_Two)_TwoSi (OC
H_Three)_Three, Toshiba Silicon KK] and Isopropyl Arco
− Le 〔(CH_Three)_TwoCHOH] and 60% nitric acid [HNO]_Three] To weight ratio
And CF_Three(CF_Two)₇(CH_Two)_TwoSi (OCH_Three)_Three: (CH_Three)_TwoCHOH: 60% HNO_Three
A coating liquid B was prepared by mixing at a ratio of 1: 25: 1.

Then, the surface of the underlayer film is coated with the cotton soaked with the coating solution B and heat-treated at about 140 ° C. for about 30 minutes to give a water-repellent film having a thickness of about 20 nm. Was formed.

Subsequently, the excess water-repellent film was wiped with cotton containing isopropyl alcohol to obtain a water-repellent oxide film on the water-repellent treated glass substrate. As a result, Example 1
When the same evaluation as above was performed, S-UV irradiation time / hr and contact angle
Fig. 2 shows the relationship of changes with time in ° C / °.
For 1 hour at ▲ mark, if the underlayer film is at 200 ℃ for 10 minutes, at ▼ mark, if the underlayer film is at 200 ℃ for 1 hour ■
The mark indicates that the underlayer film was at 300 ℃ for 10 minutes, and the mark indicates ◆, the initial contact angle was about 110 °, and the S-UV irradiation time was about 1000 hours (hr) or more. Although about 55 °, which is the same degree as that of the above-mentioned water-repellent agent directly applied to the glass surface to form a film (marked with ○), the contact angle of the present invention of this example with respect to the S-UV irradiation time ( The change in temperature (°) with time is gentle, especially under conditions of 300 ° C and 10 min, which shows markedly superior light resistance. The higher the heat treatment temperature, the more gradual the decreasing tendency. The higher the value is, for example, about 200 ° C. to 620 ° C., and particularly about 250 ° C. to 550 ° C., the light resistance is remarkably improved. It had the desired performance.

In addition to the above results, the coating liquid A
Was applied with a spin coater, dried at room temperature and then heat-treated,
The results are shown in Table 1 including the case where the water-repellent film was formed by heat treatment. From Table 1, the light resistance was significantly improved by the heat treatment of the underlayer film.

[0057]

[Table 1]

Comparative Example 1 A few drops of the same coating solution B as in Example 1 were dropped onto the surface of a glass substrate similar to that in Example 1, spread evenly using cotton, and directly coated. After repeating the operation once, the film was dried at room temperature for about 24 hours to form a water-repellent film having a thickness of about 20 nm.

The results show that in the case where the above-mentioned water repellent was directly applied to the glass surface to form a film, the relationship between the S-UV irradiation time / hr and the contact angle / ° change with time is shown by a circle in FIGS. like,
The initial contact angle is about 110 °, but the S-UV irradiation time is about
It will decrease to about 55 ° in about 450 hours (hr), and the change over time of its contact angle (°) with respect to the S-UV irradiation time will decrease sharply, and it has the desired performance of water-repellent oxidation. It was hard to say a physical film.

[0060]

As described above, according to the water-repellent oxide film of the present invention and the method for producing the same, a specific underlayer film is heat-treated by firing at a high temperature as necessary to form the film. By forming a specific water-repellent film on the substrate at room temperature to a relatively high heat treatment temperature, a water-repellent oxide film can be efficiently obtained by a simple and easy film forming means. By doing so, it is possible to form an underlayer film that remarkably enhances the adhesion between the water-repellent film and the glass surface, and a two-layer film in which the specified underlayer film is covered with the specified water-repellent film is used. By heat treatment, it exerts its performance remarkably, without impairing the optical characteristics, as well as water repellency,
The light resistance and the scratch resistance can be significantly improved, and the durability such as chemical resistance and weather resistance can be further improved.
The present invention provides a useful water-repellent oxide film and a method for producing the same, which can be suitably used for various glass articles, various building construction materials, including window materials for construction or automobiles.

[Brief description of the drawings]

FIG. 1 shows the S-UV irradiation time (hr) for the two-layer water repellent oxide film of the present invention in Example 1 and the one-layer water repellent film and the underlayer film of Comparative Example 1 only at room temperature. In the present invention, the relationship between the change in contact angle (°) and the contact angle (°) with time is indicated by ▲ when the underlayer film is at 100 ° C. for 1 hour, and the underlayer film is 200
When the temperature is 10 minutes at ℃, it is shown by ▼, when the underlayer film is at 200 ℃ for 1 hour, it is shown by ■, and when the underlayer film is at 300 ℃ for 10 minutes, it is shown by ◆, and Comparative Example 1 is indicated by ○. It is an explanatory view each shown by a mark.

FIG. 2 shows the S-UV irradiation time (hr) for the two-layer water repellent oxide film of the present invention in Example 2 and the one-layer water repellent film and the underlayer film of Comparative Example 1 only at room temperature. In the present invention, the relationship between the change in contact angle (°) and the contact angle (°) with time is indicated by ▲ when the underlayer film is at 100 ° C. for 1 hour, and the underlayer film is 200
When the temperature is 10 minutes at ℃, it is shown by ▼, when the underlayer film is at 200 ℃ for 1 hour, it is shown by ■, and when the underlayer film is at 300 ℃ for 10 minutes, it is shown by ◆, and Comparative Example 1 is indicated by ○. It is an explanatory view each shown by a mark.

Claims (13)

[Claims] 1. A silica base film formed by coating a glass substrate with a coating liquid A containing tetraisocyanate silane as a main component which cures at room temperature, drying at room temperature, and heat-treating it, and the silica base. On the water-repellent film, a coating film B made of an alkoxysilane-based water repellent having one or more side chains having a fluorocarbon group is applied and treated to be water-repellent. Characteristic water-repellent oxide film. 2. A coating solution B comprising an alkoxysilane-based water repellent having at least one side chain having a fluorocarbon group, wherein the coating liquid B is an alkoxysilane compound having at least one side chain having a fluorocarbon group, or The water-repellent oxide film according to claim 1, which is a coating liquid containing at least one of a mixture of an alkoxysilane compound having at least one side chain having a fluorocarbon group and a long-chain aliphatic silane compound. . 3. A coating solution B comprising an alkoxysilane-based water repellent having at least one side chain having a fluorocarbon group is (C _n F _{2n + 1} C ₂ H ₄ ) _a SiR ¹ _b (OR ² ) _{4-a -b} (however
R ¹ , R ² : an alkyl group, n is an integer of 1 or more. a = 1,2,3. b =
0,1,2. a + b = 1,2,3. ] The coating liquid containing alkoxysilane having at least one side chain having a fluorocarbon group represented by the following as a main component.
The water-repellent oxide film described. 4. A silica base film is formed by coating a glass substrate with a coating solution A made of a tetraisocyanate silane compound which cures at room temperature, drying at room temperature and heat treating at 700 ° C. or lower for 0.1 minute or longer. After that, a coating solution B made of an alkoxysilane-based water repellent having at least one side chain having a fluorocarbon group is applied onto the silica base film to apply water repellent treatment, and the silica base film and the silica base film are repelled. A method for producing a water-repellent oxide film, comprising forming a water-repellent oxide film composed of a laminated film of two water films. 5. The coating solution A comprises tetraisocyanate silane and a diluting solvent, and the mixing ratio thereof is a weight ratio,
The method for producing a water-repellent oxide film according to claim 4, wherein tetraisocyanate silane: diluting solvent = 1: 4 to 1: 999. 6. The repellant agent according to claim 4, wherein the heat treatment after applying the coating solution A and drying at room temperature is 0.1 minutes or more and 24 hours or less at 50 ° C. or higher and 670 ° C. or lower. Manufacturing method of aqueous oxide film. 7. The coating solution B comprising an alkoxysilane water repellent having at least one side chain having a fluorocarbon group has a solid content concentration of 0.1 to 5% by weight in terms of oxide and a viscosity. 7. The method for producing a water repellent oxide film according to claim 4, wherein the water repellent oxide film has a thickness of 0.2 to 7 cP. 8. A coating solution B comprising an alkoxysilane water repellent having at least one side chain having a fluorocarbon group, wherein the coating liquid B is an alkoxysilane compound having at least one side chain having a fluorocarbon group, or A coating solution containing at least one of a mixture of an alkoxysilane compound having one or more side chains having a fluorocarbon group and a long-chain aliphatic silane compound, wherein the side chains having a fluorocarbon group are contained in a weight ratio. 0.1 to 5 parts of one or more alkoxysilane compound, 0 to 15 long chain aliphatic silane compound
Part, diluted solution 90 to 110 parts mixed solution, acid catalyst
7. A water-repellent oxide film according to claim 4, which is a solution containing 0.1 to 5 parts by weight and 0 to 10 parts by weight of a silicon isocyanate compound, and has a viscosity of 0.5 to 6 cP. Manufacturing method. 9. A coating solution B comprising an alkoxysilane-based water repellent having at least one side chain having a fluorocarbon group is (C _n F _{2n + 1} C ₂ H ₄ ) _a SiR ¹ _b (OR ² ) _{4-a -b} (however
R ¹ , R ² : an alkyl group, n is an integer of 1 or more. a = 1,2,3. b =
0,1,2. a + b = 1,2,3. ] The coating liquid containing an alkoxysilane having at least one side chain having a fluorocarbon group represented by the following as a main component.
A method for producing the water-repellent oxide film described. 10. The method for producing a water repellent oxide film according to claim 4, wherein the heat treatment after applying the coating liquid B in the water repellent treatment is at room temperature to 400 ° C. for 0.1 minute or more. . 11. The heat treatment after applying the coating liquid B according to claim 7 is performed at 100 ° C. to 400 ° C. for 0.1 minutes to 120 minutes, and the heat treatment is performed.
11. The method for producing a water repellent oxide film according to any one of items 1 to 10. 12. The heat treatment after applying the coating liquid B according to claim 8 at room temperature to 160 ° C. for 10 minutes or more,
The method for producing a water-repellent oxide film according to any one of claims 4 to 6 and 8 to 10, which is 12 hours or more at room temperature. 13. The coating method of the coating solutions A and B is hand coating or existing coating means.
13. A method for producing a water-repellent oxide film according to any one of items 1 to 12.