JP3268012B2 - Water-repellent oxide film and method for forming the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a sol-gel film having a micropit-like surface layer, an uneven surface layer or a convex surface layer and having a controllable size as an underlayer, and a fluorocarbon film on the underlayer film. A coating solution using a fluorine-containing silane compound having a group is applied, a water-repellent oxide film formed into a laminated thin film and a method for forming the same, particularly in a multilayer film in which a film is laminated on a glass substrate,
In particular, a unique sol-gel film was used as a base film or underlayer film to coat the specified water-repellent film, so that its performance would be remarkably exhibited, such as without losing optical characteristics over a long period of time, and stubborn An object of the present invention is to provide a water-repellent oxide film which is excellent in abrasion resistance or durability due to adhesion and is useful in window materials for buildings or automobiles and various glass articles with a film, and a method for forming the same.

[0002]

2. Description of the Related Art Generally, as a method of forming irregularities on the surface of a metal oxide film, for example, a method of etching the metal oxide film with hydrofluoric acid or hydrofluoric nitric acid, or a method of burning and decomposing by heat treatment. A method of adding an organic polymer to a metal alkoxide solution and the like are known.

However, in the method of etching a metal oxide film with hydrofluoric acid or hydrofluoric nitric acid, the hydrofluoric acid or hydrofluoric nitric acid, which is an etching solution, is an extremely dangerous substance for the human body, and the handling is troublesome. In addition to the poor productivity, there is a decrease in productivity due to the addition of an etching step, and the method of adding an organic polymer that decomposes by burning to a metal alkoxide solution, for example, in the form of a micro pit once formed Since the surface is densified by heating and baking at a temperature of 400 ° C. or more, there is a restriction that the heat treatment conditions must be variously controlled, and it is difficult to obtain a stubborn film due to this restriction. However, it is not always easy.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and is intended to select a specific metal alkoxide compound or a metal acetylacetonate compound and obtain an average molecular weight of the compound. By combining different types of coating solutions with different mixing ratios and controlling the relative humidity at the time of coating, even if sintering is sufficient, independent and unique micro-pits or irregularities It has a surface layer that is variously shaped or convex and its shape and size are variously controlled, has high adhesion and has both durability and abrasion resistance, and is useful alone as a base material or lower layer, etc. The sol-gel film, which is a material thin film, can be obtained efficiently at a low cost without any troublesome steps, and with only the unique micropit-like or irregular surface. Razz is to provide a novel water-repellent oxide film and its formation method to the fluorine-containing silane compound having a specific fluorocarbon groups as allowed to cover impregnate into the inside film.

That is, the present invention provides a thin film formed on a surface of a glass substrate, wherein the thin film selects at least one or more compounds from a metal alkoxide compound or a metal acetylacetonate compound,
Moreover, the average molecular weight of the two or more selected compounds is different, and the two or more compounds are mixed with a solvent to form a coating solution, and the mixing ratio of the two or more compounds selected from the solution is adjusted. And / or a sol-gel film, which is a micropit-like surface layer, an uneven surface layer, or a convex surface layer, which is formed by coating the solution under control of relative humidity and heating to form an underlayer. A water-repellent oxide film, which is a laminated thin film formed by applying and heating a coating liquid comprising a fluorine-containing silane compound having a fluorocarbon group.

The different average molecular weights of the two or more selected compounds are as follows: one low-average molecular weight compound is thousands, and the other one or more high-average molecular weight compounds is tens of thousands to several thousands. The above-mentioned water-repellent oxide film, wherein a sol-gel film consisting of 100,000 is used as an underlayer.

Further, the mixing ratio of the selected two or more compounds is adjusted by lowering the sol-gel film consisting of 0.1 to 30 mol of the low average molecular weight compound per 1 mol of the high average molecular weight compound. The above-described water-repellent oxide coating, wherein the coating is a formation layer.

Further, the micropit-like surface layer, the uneven surface layer, or the convex surface layer has a thickness of 10 to 100 n.
The water-repellent oxide film as described above, wherein a sol-gel film having a diameter of m is used as a base layer. In addition, my
Cropit-like surface layer is a pore with an arbitrary diameter on a flat surface
And the uneven surface layer is the whole surface is uneven
Film, convex surface layer is a projection on a flat base surface
Refers to the surface layer dotted with. In addition, the diameter
In the case of a pit-shaped surface layer, it indicates the `` micro-pit pore size ''.
In the case of an uneven surface layer, it indicates "distance between peaks"
In the case of a surface layer, "distance between protrusions" is indicated.

Further, the coating solution comprising the fluorine-containing silane compound having a fluorocarbon group is an alcohol solution, and the solid content of the coating solution is 0.1 to 5 wt% in terms of oxide. Water repellent oxide coating.

Further, the above-mentioned water-repellent oxide film is characterized in that a coating solution comprising the fluorine-containing silane compound having a fluorocarbon group is applied, and the heating temperature for forming the film is 100 to 400 ° C.

A thin film is formed on the surface of a glass substrate .
The metal alkoxide-based compound or the metal acetylacetonate-based compound.
Two or more compounds having different average molecular weights are selected, the two or more compounds are mixed with a solvent to form a coating solution, and the mixing ratio of the selected two or more compounds in the solution is adjusted and / or the relative ratio is adjusted. carried out the control of humidity
To apply the coating solution to the surface of the glass substrate.
Thereafter , the applied solution is heated and formed into a film at a temperature of 100 ° C. or more, and the surface is formed into a micropit-like surface or an uneven surface, or
Form a sol-gel film as an underlayer consisting of a convex surface layer ,
On the sol-gel film, a coating solution comprising a fluorine-containing silane compound having a fluorocarbon group is applied and heated.
The fluorocarbon-containing oxide thin film is formed into a sol-gel
A method for forming a water-repellent oxide film, comprising forming a laminated thin film obtained by impregnating a film .

Two or more selected different average molecular weights
The average molecular weight of the compound is one low average molecular weight compound
Are thousands, and one or more other high average molecular weight compounds
Wherein the water repellency is tens to hundreds of thousands.
A method for forming an oxide film. In addition, the two or more selected
The mixing ratio of the compound in the solution was adjusted to the value of compound 1 having a high average molecular weight.
0.1-30 m of low average molecular weight compound based on mol
The above-mentioned water-repellent acid is adjusted in the range of ol
Method of forming oxide film. Further, the relative humidity is set to 20 to 8
Characterized in that the control is performed within a range of 0%.
A method for forming a water-repellent oxide film. Furthermore, the underlayer and
Of solids in coating solution of sol-gel film
Degree (in terms of oxide) is 0.01 to 10 wt%
The formation of a water-repellent oxide film according to claim 1,
Law. In addition, the said coating solution is 1-10C. P.
(Centipoise) to form sol-gel film by adjusting viscosity
It is characterized by the following.

The fluorine-containing compound having a fluorocarbon group
The coating liquid consisting of a silane compound is alcohol
A solution having a solid content (in terms of oxide) of 0.1 to
The above water-repellent oxide, characterized in that the content is 5 wt%.
The method of forming the coating. Also, having the fluorocarbon group
Applying coating solution consisting of fluorine-containing silane compound
And the temperature at which the film is formed by heating is 100 to 400 ° C.
The method for forming a water-repellent oxide film described above, which is characterized in that:

Here, as described above, at least one or more compounds are selected from the metal alkoxide compounds or the metal acetylacetonate compounds because both compounds are stable, In the preparation of the solution, for example, it is easy to control the average molecular weight, and the oxide thin film having various surface shapes of the formed micropit-like surface layer, the uneven surface layer or the convex surface layer has high transparency and hardness, and is durable. Both compounds are used because they are excellent in properties and relatively inexpensive and easily available.

The metal alkoxide compounds include those in which only an alkoxy group is bonded to a metal, that is, not only methoxide, ethoxide, isopropoxide and the like, but also a part of which is substituted by a methyl group, an ethyl group and the like. For example, monomethyl alkoxide, monoethyl alkoxide and the like. Further, the metal acetylacetonate-based compound includes not only a case where all acetylacetone groups are bonded to the metal but also a part of which is substituted with a methylalkoxy group, an ethylalkoxy group or the like.

Further, although not particularly specified, the metal is preferably selected from Si, Ti and Zr, and specific examples thereof include tetramethoxysilane [Si (OMe) ₄ Me: CH ₃ ], tetraethoxysilane _{[Si (OEt) 4 Et: C} 2 H 5 ],
Methyltriethoxysilane [MeSi (OEt) ₃ ],
Methyltrimethoxysilane [MeSi (OMe) ₃ ],
Titanium tetraisopropoxide [Ti (O-iso-P
r) ₄ Pr: C ₃ H ₇ ], titanium acetylacetonate [Ti (CH ₂ COCH ₂ COCH ₃ ) ₄ ], zirconium normal butoxide [Zr (On-Bu) ₄
Bu: C ₄ H ₉ ], zirconium acetylacetonate [Zr (CH ₂ COCH ₂ COCH ₃ ) ₄ ] and the like are suitable. In addition, for example, dimethyldiethoxysilane, dimethyldimethoxysilane, titanium tetranormal butoxide,
Zirconium tetraisopropoxide, zirconium tetraoctylate, and the like.

Further, the reason why the average molecular weights of the two or more selected compounds are different is that the surface layer of the coated thin film is made to have a micropit shape, an uneven shape, or a convex shape. The above compounds have an average molecular weight of several thousands (specifically, about 800 to 8000, preferably about 2000 to 7000) and tens of thousands (specifically,
000 to 70,000), or a combination of several thousand and several hundred thousand (specifically, about 100,000 to 400,000).

On the other hand, the average molecular weight is controlled by adjusting the type of catalyst (for example, hydrochloric acid, nitric acid, acetic acid, etc.) and the amount of addition, that is, the PH value (for example, PH = 1 to 4) when preparing the solution.
6, preferably 2-4) and the reaction temperature (e.g.
(80 ° C., preferably 25 to 70 ° C.) by controlling the hydrolysis reaction process or the condensation polymerization process. The average molecular weight is defined as
Nomers undergo hydrolysis and condensation polymerization reactions to produce dimers and trimers.
ー, oligomers and polystyrene equivalents when enlarged
We say child quantity. However, the reaction time and the like differ depending on the compound, and may not necessarily be common to all the compounds.

The shape of the micropit-like surface layer, the uneven surface layer or the convex surface layer can be controlled by controlling the average molecular weight of two or more kinds of compounds to be mixed in the range of thousands and tens of thousands, or thousands and hundreds of thousands. Is about 0.1 to 30 in terms of a solute molar ratio (in terms of oxide), and a flat planar shape is obtained when the mixing ratio is less than 0.1 or exceeds 30. Above all, it is preferably about 1 to 20, more preferably about 2 to 5.5 for the micropit-like surface layer, and 5.5 for the uneven surface layer.
About 5 to 7 and about 7 to 15 in the convex shape. The size of each surface layer can be controlled by the relative humidity at the time of coating.
nm, and in the case of about 80%, it is about 100 nm.

The concentration of the metal alkoxide-based compound or metal acetylacetonate-based compound in the alcohol solution is preferably about 0.01 wt% or more. It becomes increasingly difficult to form a coating having
If the content exceeds about t%, the solution becomes viscous, and although there are three types of surface layer shapes, cracks are developed and the film formation itself becomes difficult. Further, as the alcohol solvent in the present alcohol solution, methyl alcohol, isopropyl alcohol, 1-butanol, or the like can be employed.

Further, as a method for forming a film on the glass substrate, a known coating means such as a dipping method, a spray method, a flow coating method or a spin coating method can be appropriately employed. After coating with the coating solution,
Each time a thin film of the layer is formed, it is preferable to dry the film for about 30 minutes or less at an ambient temperature of about 100 ° C. to form a gel film having the above three types of surface layers.

Furthermore, the three types of surface shape surface layers of the present invention are formed due to the difference in the degree of polycondensation, and disappear due to firing (for example, at about 500 ° C. or more) for strengthening the film. No, independent pits,
The irregularity and convexity are formed up to the surface and the vicinity of the interface with the substrate, and the film is excellent in film strength, for example, it can be clearly observed at 10,000 times with a scanning electron microscope.
It can be a surface layer of any kind.

For example, in etching with HF or the like,
The structure has portions that are easily etched and portions that are not easily etched, and the portions that are easily etched are pit-shaped, so that they are rather continuous, and it is difficult to control the film thickness and pits. It is difficult to observe the pits in the pit. Also, for example, an organic substance in a sol-gel film, a solvent,
In the case of making porous by sintering of water or the like, usually 250 to 300
The whole film becomes porous once by firing at around ° C,
When calcination is performed at a temperature of not less than ° C., the film is dense and hardened, nonporous occurs at the same time, pit-shaped ones disappear on the film surface and inside, and even when observed at 30,000 to 50,000 times with a scanning electron microscope, For example, the surface shape was flat and the conventional method was clearly different from the micropit-like surface layer, the uneven surface layer or the convex surface layer of the present invention.

The fluorine-containing silane compound having a fluorocarbon group includes, for example, CF ₃ CH ₂ C
H ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ C
H ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ C
H ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ C
H ₂ CH ₃ Si (OCH ₃ ) _{2 and the} like, and CF ₃ (C
F ₂ ) ₇ CH ₂ CH ₂ SiCl ₃ or a partial hydrolyzate thereof can be used.

The solid concentration of the fluorine-containing silane compound having a fluorocarbon group in the second alcohol solution is 0.1 to 5% by weight in terms of oxide. The water repellency is insufficiently imparted, for example, the contact angle with water is about 60 to 70 °, and the water repellency no longer improves even if it exceeds 5 wt%, and the contact angle with water remains at about 110 to 115 °. This is because the above does not improve and the effect cannot be obtained.

Further, the glass substrate is an inorganic transparent plate glass, which is not particularly limited to colorless or colored, and its type, color tone, shape, and the like. Needless to say, it can be used as a glass, a strengthened glass, a flat plate or a single plate, and can also be used as a double glazing or a laminated glass.

[0027]

As described above, a water-repellent oxide film obtained by forming a sol-gel film having a micropit-like surface layer, a concavo-convex surface layer or a convex surface layer of the present invention as an underlayer thin film and forming the specified water-repellent thin film, and the same. By the formation method, two compounds of the specific system described above are selected, and at least a combination of the compounds having different average molecular weights is obtained. It has a clear and firm micropit-like, irregular or convex surface layer, and can control the shape and diameter of the three types of surface layers, improves adhesion and forms a stubborn thin film. Not only the interface of the film, but also the interface between the film and the film in the multilayer film.
It is durable, transparent and high in hardness, and it can provide satisfactory water repellency over a long period of time, as well as optical characteristics, and can be used even if it is difficult to use it outdoors. It can be obtained inexpensively and efficiently with high safety and no troublesome steps.

[0028]

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 washed sequentially with a neutral detergent, water rinse and alcohol, dried, and then wiped with acetone to obtain a glass substrate for coating.

Silicon ethoxide (average molecular weight: about 3,
20.0 g of silicon ethoxide (average molecular weight: about 100,000, solids concentration: about 6 wt%), and about 28.6 g of silicon ethoxide (solids concentration: about 30 wt%) in a beaker. / The solid content of the high average molecular weight was adjusted to a molar ratio of about 3.5, and about 50
g and 1-butanol diluted with about 100 g,
After stirring for an hour, a coating solution was obtained.

Then, the solution is coated on the surface of the glass substrate by dipping in an environment of about 23 ° C. and a relative humidity of about 50%, and heated at about 270 ° C. for about 10 minutes to form a gel film. An SiO ₂ thin film having a thickness of about 150 nm was formed. Observation of the surface shape of the thin film with a scanning electron microscope at a magnification of about 20,000 times revealed that the thin film had a micropit-like surface layer as shown in FIG.

Then, heptadecatridecylfluoroalkylsilane [CF ₃ (C ₃
1 g of F ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) _3, 48 g of isopropyl alcohol, and 1 g of 60% nitric acid were placed in a beaker, mixed and stirred well at room temperature to prepare a partially hydrolyzed solution of fluoroalkyltrimethoxysilane. Apply the thing and put it in an electric furnace set at about 250 ° C. for about 30 minutes,
Water repellency treatment was performed. The film thickness was about several tens nm.

The following test was performed on the obtained glass substrate with a laminated thin film. (Water repellency test) The contact angle to water in the atmosphere (about 25 ° C.) was measured using a CA-A type manufactured by Kyowa Interface Science.

(Durability test) The durability was evaluated by the sliding durability with a wiper blade for automobiles. Conditions: The sliding was performed about 30,000 times (one reciprocation was performed) under a load of about 105 g while dropping the tap water, and the contact angle was evaluated by the reduction amount.

As shown in Table 1, the results showed that the initial contact angle was about 113 ° and the contact angle after sliding 30,000 times of water was about 87 °, which was the expected performance. (Weather resistance test) Evaluation was made by xenon irradiation.

Conditions: about 180 w / m ² , about 1 cycle
For 80 hours, the last about 25 minutes was sprayed with clean water at a temperature of 20 ° C. The surface temperature of the glass substrate during irradiation is about 53
° C, and the change in contact angle with time was evaluated.

As a result, as shown in FIG. 9, the one having the initial contact angle of about 113 ° remained at about 85 ° even after the irradiation time of about 2,000 hours, and had the expected performance.

Example 2 On the same glass substrate as in Example 1, the silicon ethoxide used in Example 1 (average molecular weight: about 3,000, solid content concentration)
(Degree: about 30 wt%) and about 30 g of the other silicon ethoxide used in Example 1 (average molecular weight: about 100,000,
(Concentration of form: about 6 wt%) About 23.1 g was put into a beaker, and the molar ratio of the low-average molecular weight solids / the high-average molecular weight solids was about 6.5, and the other conditions were the same as in Example 1. As shown in FIG. 2, the surface layer was uneven. Next, a water-repellent treatment was performed in the same manner as in Example 1. The film thickness was about several tens nm.

The obtained glass substrate with a laminated thin film was evaluated in the same manner as in Example 1. As shown in Table 1, the durability test showed that the initial contact angle was
The contact angle after about 10,000 slides was about 75 ° and the weather resistance test showed that the initial contact angle was about 111 ° as shown in FIG. It stayed and had the expected performance.

Example 3 On the same glass substrate as in Example 1, the silicon ethoxide used in Example 1 (average molecular weight: about 3,000, solids concentration)
Degree: about 30 wt%) and about 40 g of other silicon ethoxide used in Example 1 (average molecular weight: about 100,000,
(Concentration of form: about 6% by weight) About 18.2 g was placed in a beaker, and the molar ratio of low-average molecular weight solids / high-average molecular weight solids was about 11, and the other conditions were the same as in Example 1. FIG.
As shown in FIG. Next, Example 1
Water-repellent treatment was performed in the same manner as described above. The film thickness was about several tens nm.

When the obtained glass substrate with a laminated thin film was evaluated in the same manner as in Example 1, the durability test showed that the initial contact angle was about 112 ° and the
The contact angle is about 77 ° after every sliding, and the weather resistance test shows that the initial contact angle is about 112 ° as shown in FIG. It stayed and had the expected performance.

Example 4 A coating solution used in Example 1 was used on a glass substrate similar to that in Example 1, the relative humidity during film formation was set to about 35%, and the other conditions were the same as in Example 1. As shown in FIG. 4, the surface was a micropit-like surface layer, and the pit diameter was about 10 to 20 nm. Next, a water-repellent treatment was performed in the same manner as in Example 1, and the film thickness was also about the same.

The obtained glass substrate with a laminated thin film was evaluated in the same manner as in Example 1. The durability test was as shown in Table 1, and the weather resistance test was almost the same as in Example 1. It had the performance of the period.

Example 5 A coating solution used in Example 1 was used on a glass substrate similar to that in Example 1, the relative humidity during film formation was set to about 45%, and the other conditions were the same as in Example 1. As shown in FIG. 5, the surface layer was a micropit-like surface layer, and the diameter of the pit was about 50 to 60 nm. Next, a water-repellent treatment was performed in the same manner as in Example 1, and the film thickness was also about the same.

When the obtained glass substrate with a laminated thin film was evaluated in the same manner as in Example 1, the durability test was as shown in Table 1, and the weather resistance test was almost the same as in Example 1. It had the performance of the period.

Example 6 The same coating solution as used in Example 1 was used for the same glass substrate as in Example 1, the relative humidity during film formation was set to about 70%, and the other conditions were the same as in Example 1. As shown in FIG. 6, the surface layer was in the form of micropits, and the diameter of the pits was large, and was about 100 nm or more. Next, a water-repellent treatment was performed in the same manner as in Example 1.

When the obtained glass substrate with a laminated thin film was evaluated in the same manner as in Example 1, the durability test was as shown in Table 1, and the weather resistance test was almost the same as in Example 1. It had the performance of the period.

Comparative Example 1 Silicon ethoxide (average molecular weight: about 100,000,
About 200 g of the solid content concentration (about 6 wt%) was weighed into a beaker, and used directly as a coating solution. Other than that was the same as in Example 1, and then water-repellent treatment was performed as in Example 1.

As shown in FIG. 7, the shape of the surface layer of the SiO ₂ film of the obtained film was flat, and the durability test was performed at an initial contact angle of about 110 ° as shown in Table 1 as shown in Table 1. After sliding 30,000 times with water, the contact angle was about 20 °.
As shown in the figure, the initial contact angle is about 110 °,
Even after an irradiation time of about 2,000 hours, it was about 62 °, which was far from the expected one.

Comparative Example 2 In the same manner as in Comparative Example 1, the obtained sample was added at about 0.2 wt%.
Surface treatment was performed for about 5 minutes with an aqueous HF solution. Next, a water-repellent treatment was performed in the same manner as in Example 1.

As shown in FIG. 8, the surface layer of the film after the HF treatment had an irregular shape as in Example 2. As in Comparative Example 1, the obtained product was not at all expected.

[0052]

[Table 1]

[0053]

As described above, according to the water-repellent oxide coating of the present invention and the method for forming the same, a coating can be obtained efficiently and inexpensively by a simple and easy film forming means, and the control of the coating can be achieved. By obtaining a metal oxide thin film with a stubborn micro pit shape with a unique shape and diameter, a surface layer that is uneven or convex, used as an underlayer, and impregnated with the specified water-repellent oxide thin film, Demonstrating its performance, without impairing optical properties, it will be excellent in water repellency, adhesion, scratch resistance, durability and weather resistance, etc.
The present invention provides a useful water-repellent oxide film and a method for forming the same, which can be suitably used in a sliding portion of a wiper in a window material of an automobile or the like, including a window material for a building or an automobile. .

[Brief description of the drawings]

FIG. 1 is a photograph obtained by observing the surface of a sol-gel film having a micropit-like surface layer of the present invention with a scanning electron microscope in Example 1, and is a diagram showing the state of the micropit-like surface layer in detail. .

FIG. 2 is a photograph obtained by observing a surface layer of a sol-gel film having an uneven surface layer of the present invention with a scanning electron microscope in Example 2, and is a diagram showing the state of the uneven surface layer in detail.

FIG. 3 is a photograph obtained by observing a surface layer of a sol-gel film having a convex surface layer of the present invention with a scanning electron microscope in Example 3, and is a diagram showing the state of the convex surface layer in detail.

FIG. 4 shows a relative humidity of about 35% during film formation in Example 4.
Is a photograph obtained by observing the surface layer of the sol-gel film having the micropit-like surface layer of the present invention obtained by the above with a scanning electron microscope, and shows in detail the state of the micropit-like surface layer having a pit size of about 10 to 20 nm. FIG.

FIG. 5 shows a relative humidity during film formation of about 45% in Example 5.
Is a photograph obtained by observing the surface layer of the sol-gel film having the micropit-like surface layer of the present invention obtained by the above with a scanning electron microscope, and shows in detail the state of the micropit-like surface layer having a pit size of about 50 to 60 nm. FIG.

FIG. 6 shows a relative humidity at the time of film formation of about 70% in Example 6.
FIG. 5 is a photograph obtained by observing a surface of a sol-gel film having a micropit-like surface layer of the present invention obtained by using a scanning electron microscope, and shows a detailed state of a micropit-like surface layer having a pit size of about 100 nm or more. It is.

FIG. 7 is a photograph obtained by observing the surface of a sol-gel film having a flat surface with a scanning electron microscope in Comparative Example 1, and is a diagram showing the state of the flat surface in detail.

FIG. 8 is a photograph obtained by observing a surface layer of the sol-gel film obtained in Comparative Example 1 subjected to HF treatment with a scanning electron microscope in Comparative Example 2, and is a diagram showing the state of the surface layer having an uneven surface in detail.

FIG. 9 is a view showing the results of a weather resistance test in Examples 1 to 3 and Comparative Example 1.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Osamu Takahashi 1510 Oguchicho, Matsusaka-shi, Mie Central Technical Center (72) Inventor Hiroaki Arai 1510 Oguchi-cho, Matsusaka-shi, Mie Technical Center, Central Glass (72) Inventor Shigeo Hamaguchi 1510 Oguchicho, Matsusaka City, Mie Prefecture Central Technical Center Technical Center (56) References JP-A-61-10043 (JP, A) JP-A-62-3046 (JP, A) JP-A-5-147976 (JP, A) JP-A-5-319869 (JP, A) JP-A-5-213633 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C03C 15/00-23/00

Claims (7)

(57) [Claims] 1. A method of forming a thin film on a surface of a glass substrate
In the method , at least an average of metal alkoxide compounds or metal acetylacetonate compounds is used.
Select two or more compounds having different molecular weights, mix the two or more compounds together with a solvent to form a coating solution, and adjust the mixing ratio of the selected two or more compounds in the solution or / and the relative humidity. Control of
After applying the coating solution to the surface of the glass substrate ,
The applied solution is heated and formed into a film at a temperature of 100 ° C. or more ,
Micropit-like surface, uneven surface, or convex surface
A sol-gel film is formed as a base layer composed of a layer , and a coating solution composed of a fluorine-containing silane compound having a fluorocarbon group is applied on the sol-gel film, followed by heating to form a film.
And converting the fluorocarbon-containing oxide thin film into a sol-gel film
A method for forming a water-repellent oxide film, wherein a laminated thin film formed by impregnation coating is formed. 2. The method according to claim 1, wherein the selected average molecular weights are different from each other.
The average molecular weight of the above compound is one low average molecular weight compound.
Thousands of compounds with one or more other high average molecular weight compounds
2. The article according to claim 1, wherein the number of objects is in the range of tens of thousands to hundreds of thousands.
The method for forming the water-repellent oxide film described above. 3. In a solution of the two or more selected compounds.
Mixing ratio in 1 mol of high average molecular weight compound
In the range of 0.1 to 30 mol
3. The water repellent according to claim 1, wherein the water repellent is adjusted.
Method of forming a conductive oxide film. 4. The method according to claim 1, wherein said relative humidity is in the range of 20 to 80%.
4. The method according to claim 1, wherein the control is performed.
A method for forming a water-repellent oxide film according to any of the above. 5. A coating of a sol-gel film as said underlayer.
Solids concentration (in terms of oxide) of the printing solution is 0.
3. The composition according to claim 1, wherein the content is from 0.1 to 10% by weight.
5. The method for forming a water-repellent oxide film according to any one of 4. 6. Fluorine having a fluorocarbon group
The coating solution containing the silane compound
Solution with a solid content concentration (as oxide) of 0.1
6 to 5 wt%.
A method for forming a water-repellent oxide film according to any of the above. 7. Fluorine having a fluorocarbon group
Apply a coating solution containing the silane compound
The temperature for thermal film formation is 100-400 ° C
The water-repellent oxide according to any one of claims 1 to 6,
The method of forming the coating.