JPH08292301A - Hydrophilic glass and its production - Google Patents

Abstract

PURPOSE: To provide a hydrophilic glass capable of preventing the degradation in visibility by irregular reflection of light by adhesion of water drops on its surface and a process for production of this glass. CONSTITUTION: This hydrophilic glass is formed with a metal oxide film having a film thickness in a range of 0.01 to 0.5μm on the surface of glass subjected to reflective coating on one surface of a glass base plate on the side opposite to the coated surface of the glass base plate. The hydrophilic glass described above has hydrophilic films into which at least one kind selected from a group consisting of hydrophilic org. compds. of fatty acid ester, fatty acid ether, sulfuric acid ester, ester phosphate and sulfate are incorporated in the metal oxide film in a range of 0.1 to 30 pts.wt. per 100 pts.wt. metal oxide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic glass and a method for manufacturing the same, and more particularly to a hydrophilic glass capable of preventing deterioration of visibility due to irregular reflection of light due to water droplets adhering to the surface of a door mirror or window of an automobile. Glass and its manufacturing method.

[0002]

2. Description of the Related Art Conventionally, it is possible to prevent rear visibility from being significantly reduced due to diffused reflection of light caused by water droplets adhering to the door glass of an automobile at the time of rainfall, and the inside of the window may be fogged or raindrops may be uneven on the outside. In order to prevent unpleasant sensation due to a decrease in visibility due to adherence, a method of applying a surfactant or an organic polymer having a hydrophilic functional group to a glass or window to make the surface hydrophilic is a method. Has been.

Further, the heater incorporated in the back surface of the glass heats the glass to evaporate the water droplets on the front surface, or the water repellent treatment on the glass surface and the piezoelectric vibrator or the heater on the back surface provide the scattering effect and the evaporation effect of the water droplets. A combination of them is also in practical use.

[0004]

However, the so-called anti-fog treatment in which the surface active agent is applied by spraying or the like is easily desorbed because the surface active agent is water-soluble, and the effect is relatively short. It has a drawback that it is lost (Japanese Patent Laid-Open No. 53-58492).

Further, in the method of applying hydrophilic polymer to glass to make the surface hydrophilic, it is difficult to achieve both surface hardness and the effect of preventing water droplets from adhering. The sex was insufficient.

There is also a method of using a water-absorbing polymer as the hydrophilic organic polymer, but it is necessary to lower the degree of crosslinking in order to enhance the water-absorbing ability, and the degree of crosslinking must be increased in order to enhance scratch resistance. There was a problem that it did not happen. In this case, there is also a problem that the effect of preventing water droplets decreases when the water absorption is saturated.

There is also an example in which a water-absorbing organic polymer is combined with an organic silane compound or silica fine particles in order to overcome the problem that the hydrophilic film is easily scratched (Japanese Patent Laid-Open No. Sho 5).
No. 7-72856), however, it has not been possible to obtain sufficient scratch resistance.

On the other hand, the method of heating the glass by the heater on the back surface has a problem that it takes time to remove the water droplet because the contact area of the water droplet with the glass surface is small in ordinary glass.

Further, in the method of combining the water-repellent treatment on the glass surface with the heater and the piezoelectric vibrator on the back surface, since the water-repellent property on the Teflon-treated surface has a contact angle of water of about 120 °, the piezoelectric vibrator can be used completely. In addition, it is difficult to remove water droplets, and residual water also has a problem that the heat conduction of the heater is poor and it is difficult to remove water because the contact area with the glass surface is small.

Furthermore, this method requires an expensive piezoelectric vibrator and
There is also a problem that the entire system becomes complicated due to the need for a drive circuit and the cost becomes considerably high.

Therefore, the present invention is to solve the above-mentioned problems in the prior art and has a hydrophilic glass having a rapid water drop removing effect and having sufficient scratch resistance and durability. It is intended to provide a manufacturing method.

[0012]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
In a glass having a reflective coating on one surface of a glass substrate, a metal oxide film having a film thickness in the range of 100 to 5000Å is formed on the surface of the glass substrate opposite to the coating surface. At least one selected from the group consisting of hydrophilic organic compounds such as fatty acid esters, fatty acid ethers, sulfuric acid esters, phosphoric acid esters and sulfates in the oxide film is 0.1 to 100 parts by weight of the metal oxide. This has been achieved by a hydrophilic glass characterized by being contained in an amount of 30 parts by weight and a method for producing the same.

Further, the above object of the present invention is to provide a hydrophilic film in which one or both surfaces of a glass substrate contains a sodium sulfonate compound in an amount of 5 to 50 parts by weight based on 100 parts by weight of a metal oxide. The hydrophilic glass and the method for producing the same have been achieved.

The glass substrate used in the present invention can be appropriately selected from known glass substrates and used, and examples thereof include soda lime glass.

The sol solution of the metal oxide can be prepared by appropriately selecting from known methods, for example, a metal alkoxide compound or a metal acetylacetonate can be prepared. The metal alkoxide compounds include not only compounds in which only an alkoxy group is bonded to a metal, such as methoxide, ethoxide, and isopropoxide, but also those in which a part of them is substituted with a methyl group or an ethyl group, for example, monomethylalkoxide. And those containing monoethyl alkoxide and the like.

The metal acetylacetonate compounds include not only compounds in which only acetylacetone groups are bound to the metal but also compounds in which some of them are substituted with a methylalkoxy group or an ethylalkoxy group. Can be mentioned.

Further, as the above-mentioned metals, Si, Ti,
At least one selected from the group consisting of Zr and Al can be appropriately selected as necessary. Specifically, for example, tetramethoxysilane [Si (OMe) ₄
Me: CH ₃ (hereinafter Me is CH ₃ ) and tetraethoxysilane [Si (OEt) ₄ Et: C ₂ H ₅ ] (hereinafter E
t is C ₂ H ₅ ), methyltriethoxysilane [M
e Si (OEt) ₃ ], ethyltrimethoxysilane [Et S
i (OMe) ₃ ], titanium tetraisoporoxide [Ti (O-
_{iso -Pr) 4 Pr: C 3} H 7] ( hereinafter Pr is C ₃ H _7), titanium acetylacetonate [Ti (CH ₂ C
OCH ₂ COCH _{3) 4],} zirconium n-butoxide [Zr (O-n-Bu ) 4 Bu: C 4 H 9] ( hereinafter B
u is C ₄ H ₉ ), zirconium acetylacetonate [Zr (CH ₂ COCH ₂ COCH ₃ ) ₄ ] and the like can be mentioned as suitable ones. In addition, for example, dimethylethoxysilane, dimethyldimethoxysilane, titanium tetranormal butoxide. , Zirconium tetraisopropoxide,
Zirconium tetraoctylate and the like can be mentioned.

Commercially available silica sol solutions include Super Cera (trade name manufactured by Daihachi Chemical Industry Co., Ltd.), Ceramica (trade name manufactured by Nichiban Kenkyusho), HAS (trade name manufactured by Colcoat Co., Ltd.), Atron (trade name manufactured by Nippon Soda Co., Ltd.), CGS-D1-0600 (product number manufactured by Chisso Co., Ltd.) and the like can be mentioned.

Ti, Zr, which is used to form a multi-component system,
As the compound of Al, in addition to the alkoxides and acetylacetonates of the above-mentioned metals, at least one selected from the group consisting of various chlorides of Ti, Zr and Al, nitrates and sulfates, or their Examples include polycondensation products. Further, as a commercially available sol solution, TA-
10, TA-15 (product number manufactured by Nissan Chemical Industries, Ltd.), titania sol, NZS-30A, NZS-3
0B (product number manufactured by Nissan Chemical Industries, Ltd.) and AZS-
Examples thereof include zirconia sol such as A, AZS-NB, and AZS-B (product number manufactured by Nippon Shokubai Chemical Co., Ltd.).

Silica may be used alone as the above-mentioned metal oxide, but by using a multi-component system of at least one selected from the group consisting of titania, zirconia and alumina, more excellent scratch resistance can be obtained. Is obtained.

As the organic compound dispersed in the hydrophilic film,
For example, glycerin fatty acid ester, sorbitan fatty acid ester, fatty acid ester or ether of polyethylene glycol, fatty acid ester of sorbitol ethylene oxide adduct, higher alcohol oxycarboxylic acid ester, cyanoethylated or carbamoylethylated fatty acid ester of polyhydric alcohol, sorbitan higher fatty acid At least one selected from the group consisting of ethylene oxide adducts of esters, alkyl sulphates, alkylallyl sulphates and alkylamine sulphates.

The amount of the above-mentioned organic compound added to the sol solution of the metal oxide is 0.
It is preferably in the range of 1 to 30 parts by weight. If the amount added is less than 0.1 part by weight, sufficient hydrophilicity cannot be obtained,
On the other hand, if it exceeds 30 parts by weight, film hardening is reduced and scratch resistance becomes insufficient.

Further, in the present invention, as the component for forming the hydrophilic film, a sodium sulfonate compound can be used in place of the above hydrophilic organic compound. As the sodium sulfonate compound, it is preferable to use at least one compound selected from the following Chemical Formula 2.

[0024]

Embedded image

Examples of the sulfonic acid compound represented by the above chemical formula 2 are Perex (trade name of Kao Corporation), Latemur (trade name of Kao Corporation), NIKKOL C.
MT, NIKKOL LMT, NIKKOL MMT,
NIKKOL PMT, NIKKOL SMT, NIK
KOL OTP, NIKKOL LSA, NIKKOL
OS (trade name of Nikko Chemicals Co., Ltd.) and the like can be mentioned.

The amount of the sulfonic acid compound added to the metal oxide is 5 to 5 parts by weight based on 100 parts by weight of the metal oxide.
A ratio of 0 parts by weight is good. If the addition amount is less than 5 parts by weight, sufficient hydrophilicity cannot be obtained, and conversely, if it exceeds 50 parts by weight,
The film hardness is reduced and the scratch resistance is insufficient. In addition to the above compounds, various surfactants can be added to the sol solution of metal oxide.

When the surface of the glass substrate is subjected to the hydrophilic treatment, the above composition may be used as it is, but the composition blended in the above ratio may be used so that the solid content concentration is in the range of 0.5 to 5% by weight. A coating solution diluted with water and / or an organic solvent may be used. The composition of the coating solution is in the range of 0.3 to 5% by weight of metal oxide, 0.02 to 2% by weight of sodium sulfonate compound, and 95 to 99.5% by weight of water and / or organic solvent. It is preferable that

As the organic solvent used here, a solvent compatible with the composition such as a metal oxide, a sodium sulfonate compound and a surfactant can be preferably used. Examples of such organic solvents include primary alcohols such as methanol, ethanol or propyl alcohol, secondary alcohols such as isopropyl alcohol, tertiary alcohols such as tert-butanol, ketones such as acetone or methyl ethyl ketone, ethers, Benzene, toluene, xylene, chloroform, pentane, hexane,
Typical solvents include aliphatic, aromatic and alicyclic hydrocarbons such as cyclohexane, and these solvents can be used alone or in combination.

As a method for applying the above-mentioned metal oxide solution to which the organic compound has been added onto the glass substrate, a known method can be appropriately selected and used, for example, a dipping and pulling method (a dipping method). , A spray method, a flow coating method, a spin coating method and the like. At this time, it is necessary to form the coating film thickness after firing in the range of 100 to 5000Å. When the coating film thickness is less than 100Å, the sustainability of the hydrophilic effect becomes poor. On the contrary, if the film thickness exceeds 5000 Å, cracks occur in the film during baking.

The hydrophilic film may be formed so as to have a smooth surface, but when it is formed so as to have fine irregularities, a film having a greater hydrophilic effect and excellent durability can be obtained. Examples of the method for forming the uneven surface include a method in which two or more kinds of materials having different average molecular weights are combined and used as a sol solution of a metal oxide. As a combination of two or more kinds with different average molecular weight,
For example, it is preferable to use a combination of thousands and tens of thousands, and thousands and hundreds of thousands. The pitch of the surface irregularities is 500.
It is preferably nm or less. When it exceeds 500 nm, the scattering of visible light becomes large and the transparency of the film is impaired.

In producing the hydrophilic glass of the present invention, the above coating liquid is applied onto a glass substrate and then heated at a temperature not higher than the decomposition temperature of the added organic compound to give a hydrophilic film on the glass substrate. Can be formed. Further, by irradiating light such as ultraviolet rays after coating to polycondense the metal oxide, a hydrophilic film having more excellent scratch resistance can be obtained.

Among the sodium sulfonate compounds shown in Chemical formula 2 above, for example,

Embedded image The compound represented by (3) is easily crystallized when dried, and is difficult to form into a transparent film as it is, but a transparent hydrophilic film can be obtained by forming a film by the above method. The hydrophilic coating according to the invention can be processed both on transparent glass substrates and on the surface of glass with a reflective coating on the back side.

According to the hydrophilic glass of the present invention, various ester-based or sulfate-based organic compounds are dispersed in the metal oxide film, so that the surface tension of water is reduced to a very small value. Therefore, the visibility is not deteriorated even if it spreads thinly and water drops adhere to it. In addition, the composition of the hydrophilic film is composed only of a metal oxide and a low molecular weight organic compound,
Since it does not contain a water-absorbing polymer, excellent scratch resistance can be obtained.

Further, according to the hydrophilic glass of the present invention, since the sodium sulfonate compound is dispersed in the metal oxide film, a transparent hydrophilic film can be obtained, and the surface tension of water is lowered to spread thinly. Even if water droplets adhere, the visibility does not deteriorate. Furthermore, since the hydrophilic film is composed only of the metal oxide film and the sodium sulfonate compound and contains no water-absorbing polymer, excellent scratch resistance can be obtained.

[0035]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention.

Example 1 Size 100 mm × 100 m
A clear float glass substrate having a thickness of m and a thickness of 1.9 mm was sequentially washed with a neutral detergent, water and ethanol, and dried to obtain a coating substrate. Next, 0.15 was added to a mixed solution of 50 g of 3-aminopropyltriethoxysilane and 78 g of methanol.
20 g of a mol / L hydrochloric acid aqueous solution was added, and the mixture was reacted in a water bath at 80 ° C. for 2 hours. After cooling, 78 g of distilled water was added for pH adjustment and the mixture was stirred to obtain a silica sol solution having a solid content concentration of 6% by weight.

Glycerin fatty acid ester (trade name: Exel O-9, manufactured by Kao Corporation) was added to the obtained silica sol solution.
5R) was dispersed at a ratio of 3 parts by weight with respect to 100 parts by weight of silica, and further diluted with methanol so that the solid content concentration was 1.2% by weight to obtain a coating liquid. This coating liquid was applied on the surface of a glass substrate by a flow coating method, dried, and then baked at 200 ° C. for 30 minutes to form a hydrophilic film having a film thickness of about 0.1 μm.

Then, chromium was vapor-deposited on the surface opposite to the base layer in a vacuum vapor deposition tank. Water was sprayed on the surface of the hydrophilic glass thus obtained, video recording was performed with the surface illuminated, and the amount of water droplets attached was quantified by binarizing it by image processing. At this time, the amount of water droplets deposited was 1.5%, which was an extremely small area ratio to the whole. From this state, a 100 W heater arranged so as to be in contact with the glass surface was energized and heated. When the area ratio of water droplets after 1 minute was determined by the same method as described above, it was reduced to 0.5%.

Using a traverse tester, a load of 19.6 kPa (0.2 kgf / cm ² ) was applied to the flannel, and a speed of 1 time / sec.
A round test was conducted, but no scratches were observed on the surface.
Furthermore, as a result of measuring the amount of adhered water droplets after carrying out the traverse test, the increase was 2.0%, which was a slight increase.

Example 2 Silica / zirconia = 85 /
Adjusted to 33 (mol%) by using 3-aminopropyltriethoxysilane as a starting material, 33 g of a mixed solution of water and methanol of pH 9 and a solid content concentration of 6% by weight of silica sol, and zirconium oxychloride as a starting material. 17 g of an aqueous solution of zirconia sol having a pH of 3 and a solid content of 6% by weight was mixed to obtain a silica-zirconia solution having a pH of 4.

Glycerin monostearate was added to the obtained silica-zirconia solution by silica-zirconia 1
A coating solution was prepared by adding 15 parts by weight to 00 parts by weight and further diluting it with isopropyl alcohol so that the solid content was 1% by weight. Then
The obtained coating solution was filtered with a membrane filter having a pore size of 1 μm, and applied on a glass substrate by the flow coating method in the same manner as in Example 1. This glass substrate is 200 ℃
And was baked for 30 minutes to form a hydrophilic film having a film thickness of about 0.1 μm.

After that, chromium vapor deposition was carried out under the same conditions as in Example 1, and an evaluation test of adhered water was conducted. As a result, the initial amount of water droplets deposited was 0.8%, and the amount of water droplets deposited 1 minute after the heater was energized was 0.6%. In addition, the traverse test was conducted in the same manner as in Example 1, but no scratch was observed on the surface. In addition, the water droplet adhesion amount after the traverse test was 2.5%, which was a slight increase.

Example 3 About 20 g of silica sol (average molecular weight: about 3000, solid content concentration: about 30% by weight) and silica sol (average molecular weight: about 100,000, solid content concentration:
About 6% by weight) About 28.6 g was added to a beaker, and the low-average molecular weight solid content / high-average molecular weight solid content was about 3.5 m.
The ol ratio is about 50 g of isopropyl alcohol and 1-
Diluted with about 100 g of butanol and stirred for about 15 hours to obtain a silica solution.

Glycerin fatty acid ester (trade name: Exel O-95 manufactured by Kao Corporation) was added to the obtained silica solution.
F) was added in an amount of 0.1 part by weight based on 100 parts by weight of silica. Further, a coating solution was prepared by diluting it with isopropyl alcohol so that the total solid content concentration was 2.4% by weight. The obtained coating liquid was applied onto a glass substrate by a flow coating method as in Example 1.
This glass substrate was baked at 200 ° C. for 30 minutes to form a hydrophilic film so that the film thickness was about 0.3 μm.

Observation of the surface of the obtained hydrophilic film with a scanning electron microscope revealed that fine irregularities were formed.
The pitch of the irregularities was about 200 nm. Chromium vapor deposition was carried out under the same conditions as in Example 1, and an evaluation test of adhered water was conducted. As a result, the initial amount of water droplets deposited was 2.5%, and the amount of water droplets deposited 1 minute after the heater was energized was 2%. Further, the same traverse test as in Example 1 was carried out, but no scratch on the surface was observed. In addition, the water drop adhesion amount after carrying out the traverse test was 4.5%, which was a slight increase.

Example 4 In a silica solution obtained by the same method as in Example 1, titania sol (manufactured by Nissan Chemical Industries, Ltd., product number: TA-15) was added in a silica / titania weight ratio of 95/5. Mixed so that Glycerin fatty acid ester (trade name: Exel O-95F manufactured by Kao Corporation) was added to this sol solution so that the total solid content was 1 part by weight based on 100 parts by weight of silica-titania.
It was diluted with isopropyl alcohol so as to have a weight%.

The above coating solution was applied onto a glass substrate by the flow coating method as in Example 1. This glass substrate is baked at 200 ° C. for 30 minutes to give a film thickness of about 0.12 μm.
A hydrophilic film was formed so that After that, chromium vapor deposition was performed under the same conditions as in Example 1, and an evaluation test of adhered water was performed. As a result, the initial amount of water droplets deposited was 1.7%, and the amount of water droplets deposited 1 minute after the heater was energized was 1%.

A traverse test was carried out in the same manner as in Example 1, but no scratches were observed on the surface. Furthermore,
The water drop adhesion amount after the traverse test was 3%, which was a slight increase.

Example 5 A silica solution obtained by the same method as in Example 1 was mixed with alumina sol (product number: AS-100 manufactured by Nissan Chemical Industries, Ltd.) at a silica / alumina weight ratio of 88/12. Mixed so that Glycerin fatty acid ester (trade name of Kao Corporation:
Exel O-95F) was added to 30 parts by weight with respect to 100 parts by weight of silica-alumina, and further diluted with isopropyl alcohol so that the total solid content was 0.1% by weight.

The above coating solution was applied onto a glass substrate by the flow coating method as in Example 1. This glass substrate is baked at 200 ° C. for 30 minutes to give a film thickness of about 0.01 μm.
A hydrophilic film was formed so that

After that, chromium was vapor-deposited under the same conditions as in Example 1, and an evaluation test of adhered water was conducted. As a result, the initial amount of water droplets deposited was 0.6%, and the amount of water droplets deposited 1 minute after the heater was energized was 0.5%. In addition, the traverse test was conducted in the same manner as in Example 1, but no scratch was observed on the surface. Further, the water droplet adhesion amount after conducting the traverse test was 1.3%, which was a slight increase.

Example 6 In a silica solution obtained by the same method as in Example 1, titania sol (manufactured by Nissan Chemical Industries, Ltd., product number: TA-15) was added in a silica / titania weight ratio of 95/5. Mixed so that Glycerin fatty acid ester (trade name, manufactured by Kao Corporation: Exel O-95F) was added to this sol solution so that the total solid content was 3.8 parts by weight with respect to 100 parts by weight of silica-titania. It was diluted with isopropyl alcohol so that it became%.

The above coating solution was applied onto a glass substrate by the flow coating method as in Example 1. The glass substrate was baked at 200 ° C. for 30 minutes to form a hydrophilic film having a film thickness of about 0.5 μm.

After that, chromium vapor deposition was carried out under the same conditions as in Example 1, and an evaluation test of adhered water was carried out. As a result, the initial amount of water droplets deposited was 1.2%, and the amount of water droplets deposited 1 minute after the heater was energized was 0.7%. A traverse test was conducted in the same manner as in Example 1, but scratches on the surface were hardly recognized. In addition, the water drop adhesion amount after the traverse test was 1.7%, which was a slight increase.

Example 7 Polyoxyethylene allyl glycidyl nonylphenyl ether sulfate ester salt was added to a silica solution obtained by the same method as in Example 1 on silica 10.
It was added so as to be 2 parts by weight with respect to 0 parts by weight, and further diluted with isopropyl alcohol so that the total solid content was 1% by weight.

The above coating solution was applied onto a glass substrate by the flow coating method as in Example 1. This glass substrate is baked at 200 ° C. for 30 minutes to give a film thickness of about 0.12 μm.
A hydrophilic film was formed so that

After that, chromium vapor deposition was carried out under the same conditions as in Example 1, and an evaluation test of adhered water was carried out. As a result, the initial amount of deposited water droplets was 1.6%, and the amount of deposited water droplets 1 minute after energizing the heater was 1.5%. In addition, the traverse test was conducted in the same manner as in Example 1, but no scratch was observed on the surface. Further, the water droplet adhesion amount after the traverse test was 2.4%, which was a slight increase.

Example 8 In a silica solution obtained by the same method as in Example 1, glycerin fatty acid ester (trade name: Exel O-95F manufactured by Kao Corporation) was added to silica 10.
5 parts by weight was added to 0 parts by weight, and further diluted with isopropyl alcohol so that the total solid content was 1.2% by weight.

The above coating liquid was applied onto a glass substrate by the flow coating method as in Example 1. After film formation,
Ultraviolet rays of 254 nm and 184 nm were irradiated using a mercury lamp. Then, the glass substrate was baked at 200 ° C. for 30 minutes to form a hydrophilic film having a film thickness of about 0.12 μm.

After that, chromium vapor deposition was carried out under the same conditions as in Example 1, and an evaluation test of adhered water was carried out. As a result, the initial amount of water droplets deposited was 1%, and the amount of water droplets deposited 1 minute after the heater was energized was 0.6%. Further, the traverse test was carried out in the same manner as in Example 1, but no scratch on the surface was observed. Further, the water droplet adhesion amount after conducting the traverse test was 1.3%, which was a slight increase.

Comparative Example 1 Glycerin monostearate was added to a sol of silica prepared in the same manner as in Example 1 so as to be 3 parts by weight with respect to 100 parts by weight of silica, and isopropyl alcohol was added as a solid. Minute is 0.0
The coating solution was diluted to 5% by weight. Then, this solution was filtered with a membrane filter having a pore size of 1 μm, and applied on a glass substrate by the flow coating method as in Example 1. This glass substrate at 230 ℃ 3
It was baked for 0 minutes to form a hydrophilic film. When the film thickness was measured with a stylus type film thickness meter, the film thickness was 0.01 μm or less, and the thickness could not be detected.

After that, chromium vapor deposition was carried out under the same conditions as in Example 1, and an evaluation test of adhered water was carried out. As a result, the initial water drop deposition amount was 2%, and the water drop deposition amount 1 minute after the heater was energized was 1.4%. In addition, the traverse test was conducted in the same manner as in Example 1, but no scratch was observed on the surface. However, the water drop adhesion amount after the traverse test was significantly increased to 8%.

Comparative Example 2 Glycerin monostearate was added to a sol solution of silica prepared in the same manner as in Example 1 so as to be 3 parts by weight with respect to 100 parts by weight of silica, and solid content was further added with isopropyl alcohol. Was diluted to 8% by weight to obtain a coating solution. Then, this solution was filtered with a membrane filter having a pore size of 1 μm, and applied on a glass substrate by the flow coating method as in Example 1. This glass substrate was baked at 230 ° C. for 30 minutes to form a hydrophilic film. When the film thickness was measured by a stylus type film thickness meter, the film thickness was 0.65 μm, and cracks were generated in the film as a whole, and it could not be said that the film had good transparency.

Comparative Example 3 Glycerin monostearate was added to a silica sol prepared in the same manner as in Example 1 so as to be 40 parts by weight with respect to 100 parts by weight of silica, and solid content was further added with isopropyl alcohol. Is 1% by weight
What was diluted so that it became a coating solution.
Then, this solution was filtered with a membrane filter having a pore size of 1 μm, and applied on a glass substrate by the flow coating method as in Example 1. The glass substrate was baked at 200 ° C. for 30 minutes to form a hydrophilic film. When the film thickness was measured by a stylus type film thickness meter, the film thickness was 0.15 μm.

Thereafter, chromium was vapor-deposited under the same conditions as in Example 1, and an evaluation test of the adhered water was conducted. As a result, the initial amount of water droplets deposited was 0.4%, and the amount of water droplets deposited one minute after the heater was energized was also 0.4%. However, when the same traverse test as in Example 1 was carried out, the surface had considerably noticeable scratches, and the hardness was insufficient.

[Comparative Example 4] Glycerin monostearate was added to a silica sol solution prepared in the same manner as in Example 1 so as to be 0.05 part by weight with respect to 100 parts by weight of silica, and isopropyl alcohol was further added. A coating solution was prepared by diluting the solid content to 1% by weight. Then, this solution was filtered with a membrane filter having a pore size of 1 μm, and applied on a glass substrate by the flow coating method as in Example 1. This glass substrate was baked at 230 ° C. for 30 minutes to form a hydrophilic film. When the film thickness was measured with a stylus type film thickness meter, the film thickness was 0.12 μm.

Thereafter, chromium was vapor-deposited under the same conditions as in Example 1, and an evaluation test of the adhered water was conducted. As a result, the initial amount of deposited water droplets was as high as 5%, and the amount of deposited water droplets 1 minute after the heater was energized was 1.2%. Further, the same traverse test as in Example 1 was carried out, but no scratch on the surface was observed. However, the amount of water droplets deposited after the traverse test was significantly increased to 13%.

The compositions of Examples 1 to 8 and Comparative Examples 1 to 4 are shown in Table 1.

[Table 1]

Reference Example 1 Size 100 mm × 100 m
A glass substrate having a thickness of m and a thickness of 1.9 mm was sequentially washed with a neutral detergent, water and ethanol, and dried to obtain a coating substrate. After performing chromium vapor deposition treatment on one surface of this glass in a vacuum chamber, 1 stock solution of liquid superabsorbent polymer (trade name: Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) was applied on the other surface.
Spin coated at 000 rpm for 20 seconds. This was heated at 100 ° C. for 1 hour, and the stock solution was post-cured to form a layer of a water-insoluble superabsorbent polymer.

The initial amount of water droplets deposited on the hydrophilic glass thus obtained was 0.8%, and the amount of water droplets deposited one minute after energizing the heater was 0.3%. However, when the surface of this hydrophilic glass was subjected to the same traverse test as in Example 1, spider-like scratches were easily generated and the scratch resistance was extremely poor.

Reference Example 2 Size 100 mm × 100 m
A glass substrate having a thickness of m and a thickness of 1.9 mm was sequentially washed with a neutral detergent, water and ethanol, and dried to obtain a coating substrate. Chromium vapor deposition treatment was performed on one surface of this glass in a vacuum chamber, and then a commercially available water repellent agent (trade name: Rain X, manufactured by Unelco USA, Inc.) was applied on the other surface. An evaluation test was conducted. The initial amount of water droplets deposited was 75.1%,
The amount of water droplets deposited after 1 minute of energizing the heater was 72.2%, and the effect of the heater was hardly recognized.

Example 9 A clear float glass substrate having a size of 100 mm × 100 mm and a thickness of 1.9 mm was sequentially cleaned with a neutral detergent, water and ethanol and dried to obtain a coating substrate. The above-mentioned substrate was coated with chrome by a reflective coating to obtain glass. The surface opposite to the plated surface was polished with an abrasive, washed with water, and then cleaned with acetone. 50 g of 3-aminopropyltriethoxysilane and 78 of methanol
0.15 mol / L hydrochloric acid aqueous solution 20 in a mixed solution with g
g was added, and the mixture was reacted in a water bath at 80 ° C. for 2 hours. After cooling, 78 g of distilled water was added and stirred for pH adjustment to obtain a silica sol solution having a solid content concentration of 6% by weight.

N-acylmethyltaurine (NIKKOL-LMT, trade name of Nikko Chemicals Co., Ltd.) as a sodium sulfonate compound was dispersed in the obtained silica gel solution at a ratio of 20 parts by weight to 100 parts by weight of silica. Then, a coating liquid was prepared by further diluting it with a mixed solvent of isopropyl alcohol and water of 8: 1 so that the solid content concentration was 2% by weight. This coating liquid was applied to the surface of the glass substrate opposite to the plated surface by a flow coating method, dried and then baked at 200 ° C. for 30 minutes to form a transparent hydrophilic film having a thickness of about 100 nm.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 90 seconds after spraying water, the water film became thin and uniform, and the image on the glass became very clear. The same evaluation was performed after immersing this glass in water for 1 hour, but the time until the image reflected on the glass became visible clearly was 120 seconds, and the deterioration of hydrophilicity was very slight. Also, using a traverse tester, the flannel was 19.6 kPa (0.
The test was conducted 60 times with a load of ² kgf / cm ² ) at a speed of once / second and a stroke of 100 mm, but no conspicuous scratches were generated on the surface.

[Example 10] To a silica sol prepared in the same manner as in Example 9, sodium di (2-ethylhexyl) sulfosuccinate (NIKKOL OTP-100, trade name, manufactured by Nikko Chemicals Co., Ltd.) was used as a sodium sulfonate compound. A coating solution was prepared by dispersing 20 parts by weight with respect to 100 parts by weight and further diluting it with a mixed solvent of isopropyl alcohol and water of 8: 1 so that the solid content concentration was 1.5% by weight. . This coating liquid was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by flow coating,
After drying, baking was performed at 200 ° C. for 30 minutes to form a transparent hydrophilic film having a film thickness of about 70 nm.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 30 seconds after spraying water, the water film became thin and uniform, and the image on the glass became very clear. The same evaluation was performed after immersing the glass in water for 1 hour, but the time until the image reflected on the glass became visible clearly was 50 seconds, and the deterioration of hydrophilicity was very slight. In addition, using a traverse tester, the flannel was 19.6 kPa (0.2
A load of kgf / cm ² ) was applied and a test was performed 60 times at a speed of once / second and a stroke of 100 mm, but no conspicuous scratches were generated on the surface.

Example 11 A silica sol prepared in the same manner as in Example 9 was mixed with sodium lauryl sulfoacetate (NIKKOL LSA) as a sodium sulfonate compound.
Nikko Chemicals Co., Ltd. product name) silica 100
A coating solution was prepared by dispersing 20 parts by weight with respect to parts by weight and further diluting with a mixed solvent of isopropyl alcohol and water of 8: 1 so that the solid content concentration was 4% by weight. This coating solution was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method, dried and then baked at 200 ° C. for 30 minutes to give a film thickness of about 500 nm. A transparent hydrophilic film was formed.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 60 seconds after spraying water, the water film became thin and uniform, and the image on the glass became very clear. The same evaluation was performed after immersing this glass in water for 1 hour, but the time until the image reflected on the glass became clear was 90 seconds, and the deterioration of hydrophilicity was very slight. In addition, using a traverse tester, the flannel was 19.6 kPa (0.2
A load of kgf / cm ² ) was applied and a test was performed 60 times at a speed of once / second and a stroke of 100 mm, but no conspicuous scratches were generated on the surface.

Example 12 In a silica sol prepared in the same manner as in Example 9, sodium dodecenyl monosulfonate as a sodium sulfonate compound was dispersed at a ratio of 20 parts by weight with respect to 100 parts by weight of silica. A coating solution was prepared by diluting with a mixed solvent of isopropyl alcohol and water at an ratio of 8: 1 so that the solid content concentration was 0.7% by weight. This coating liquid was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method, dried and then baked at 200 ° C. for 30 minutes to give a film thickness of about 10 nm. A transparent hydrophilic film was formed.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 90 seconds after spraying water, the water film became thin and uniform, and the image on the glass became very clear. The same evaluation was performed after immersing this glass in water for 1 hour, but the time until the image reflected on the glass became visible clearly was 120 seconds, and the deterioration of hydrophilicity was very slight. Also, using a traverse tester, the flannel was 19.6 kPa (0.
The test was conducted 60 times with a load of ² kgf / cm ² ) at a speed of once / second and a stroke of 100 mm, but no conspicuous scratches were generated on the surface.

Example 13 To a silica sol prepared in the same manner as in Example 9, sodium hydroxydodecyl sulfonate as a sodium sulfonate compound was added to silica 10.
A coating liquid was prepared by dispersing 20 parts by weight with respect to 0 parts by weight and further diluting it with a mixed solvent of isopropyl alcohol and water of 8: 1 so that the solid content concentration was 2% by weight. This coating liquid was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method, dried and then baked at 200 ° C. for 30 minutes to give a film thickness of about 100 nm. A transparent hydrophilic film was formed.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 60 seconds after spraying water, the water film became thin and uniform, and the image on the glass became very clear. The same evaluation was carried out after immersing this glass in water for 1 hour, but the time until the image on the glass became visible clearly was 80 seconds, and the deterioration of hydrophilicity was very slight. In addition, using a traverse tester, the flannel was 19.6 kPa (0.2
A load of kgf / cm ² ) was applied and a test was performed 60 times at a speed of once / second and a stroke of 100 mm, but no conspicuous scratches were generated on the surface.

[Example 14] To a silica sol prepared in the same manner as in Example 9, sodium di (2-ethylhexyl) sulfosuccinate (NIKKOL OTP-100, trade name, manufactured by Nikko Chemicals Co., Ltd.) was used as a sodium sulfonate compound. A coating liquid was prepared by dispersing 5 parts by weight with respect to 100 parts by weight, and further diluting with a mixed solvent of isopropyl alcohol and water of 8: 1 so that the solid content concentration was 2% by weight. This coating solution was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method, dried, and baked at 200 ° C. for 30 minutes to give a film thickness of about 1
A 00 nm transparent hydrophilic film was formed.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 80 seconds after spraying water, the water film became thin and uniform, and the image reflected on the glass became very clear. The same evaluation was performed after immersing this glass in water for 1 hour, but the time until the image reflected on the glass became visible clearly was 120 seconds, and the deterioration of hydrophilicity was very slight. Also, using a traverse tester, the flannel was 19.6 kPa (0.
The test was conducted 60 times with a load of ² kgf / cm ² ) at a speed of once / second and a stroke of 100 mm, but no conspicuous scratches were generated on the surface.

Example 15 To a silica sol prepared in the same manner as in Example 9, sodium di (2-ethylhexyl) sulfosuccinate (NIKKOL OTP-100, trade name, manufactured by Nikko Chemicals Co., Ltd.) was used as a sodium sulfonate compound. A coating liquid was prepared by dispersing 50 parts by weight with respect to 100 parts by weight and further diluting with a mixed solvent of isopropyl alcohol and water of 8: 1 so that the solid content concentration was 2% by weight. This coating liquid was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method, dried and then baked at 200 ° C. for 30 minutes to give a film thickness of about 100 nm. A transparent hydrophilic film was formed.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 15 seconds after spraying water, the water film became thin and uniform, and the image on the glass became very clear. The same evaluation was carried out after immersing this glass in water for 1 hour, but the time until the image on the glass became visible clearly was 30 seconds, and the deterioration of hydrophilicity was very slight. In addition, using a traverse tester, the flannel was 19.6 kPa (0.2
A load of kgf / cm ² ) was applied and a test was performed 60 times at a speed of once / second and a stroke of 100 mm, but no conspicuous scratches were generated on the surface.

Example 16 A dispersion solution of colloidal silica (Snowtex-O Nissan Chemical Industries, Ltd.) such that the silica sol prepared in the same manner as in Example 9 is 25 parts by weight with respect to 75 parts by weight of colloidal silica. (Trade name) manufactured by Kato Co., Ltd. is further added to this solution as a surfactant.
It was added to 5 parts by weight with respect to 0 parts by weight and stirred for 15 minutes. In a mixed solution of the above silica and a surfactant, sulfosuccinic acid di (2-
Ethylhexyl) sodium (NIKKOL OTP-
100 parts of Nikko Chemicals Co., Ltd.) is dispersed in a ratio of 15 parts by weight to 100 parts by weight of silica, and further 8: 1 mixture of isopropyl alcohol and water is added so that the solid content concentration becomes 2% by weight. What was diluted with the solvent was used as the coating liquid. This coating liquid was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method, dried, and then at 200 ° C. for 3 days.
Firing was performed for 0 minutes to form a transparent hydrophilic film having a film thickness of about 150 nm.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 20 seconds after spraying water, the water film became thin and uniform, and the image reflected on the glass became very clear. The same evaluation was carried out after immersing the glass in water for 1 hour, but the time until the image on the glass became visible clearly was 20 seconds, and there was almost no deterioration in hydrophilicity. Also, using a traverse tester, the flannel has 19.6 kPa (0.2 kg
The test was conducted 60 times with a load of f / cm ² ) at a speed of once / second and a stroke of 100 mm, but no noticeable scratches were generated on the surface.

Example 17 Silica sol (average molecular weight:
Approximately 3000, solid content concentration: about 30% by weight) About 20 g and silica sol (average molecular weight: about 100,000, solid content concentration: about 6% by weight) About 28.6 g were charged into a beaker, and low average molecular weight solid content / high Approximately 3.5 solids of average molecular weight
As a molar ratio of about 50 g of isopropyl alcohol and about 100 g of 1-butanol, the mixture was stirred for about 15 hours to obtain a silica solution.

Sodium di (2-ethylhexyl) sulfosuccinate (NIKKOL OTP-100, trade name, manufactured by Nikko Chemicals Co., Ltd.) as a sodium sulfonate compound was added to the obtained silica solution in an amount of 20 parts by weight per 100 parts by weight of silica. So added. Further, a coating solution was prepared by diluting it with isopropyl alcohol so that the total solid content concentration was 2.4% by weight. The obtained coating liquid was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method. Baking at 200 ℃ for 30 minutes, the film thickness is about 3
A 00 nm transparent hydrophilic film was formed. When the surface of the obtained hydrophilic film was observed with a scanning electron microscope, fine irregularities were formed, and the irregularity pitch was about 200 nm.

Water was sprayed onto the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 20 seconds after spraying water, the water film became thin and uniform, and the image reflected on the glass became very clear. The same evaluation was carried out after immersing this glass in water for 1 hour, but the time required for the image on the glass to appear clear was 25 seconds, and there was almost no deterioration in hydrophilicity. Also, using a traverse tester, the flannel has 19.6 kPa (0.2 kg
The test was conducted 60 times with a load of f / cm ² ) at a speed of once / second and a stroke of 100 mm, but no noticeable scratches were generated on the surface.

[Example 18] TA-10 (product number manufactured by Nissan Chemical Industries, Ltd.) as a titania sol was added to silica sol prepared in the same manner as in Example 9, and the mixing ratio of silica and titania was 90:10 by weight. So that the sodium sulfonate compound is di (2-ethylhexyl) sodium sulfosuccinate (NIKKOL O
TP-100 manufactured by Nikko Chemicals Co., Ltd.) was dispersed at a ratio of 20 parts by weight with respect to 100 parts by weight of a mixture of silica and titania, and a solid content concentration was 2% by weight.
Was diluted with a mixed solvent of isopropyl alcohol and water of 8: 1 to obtain a coating liquid. This coating solution was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method, dried, and baked at 200 ° C. for 30 minutes to give a film thickness of about 1
A 00 nm transparent hydrophilic film was formed.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 15 seconds after spraying water, the water film became thin and uniform, and the image on the glass became very clear. The same evaluation was carried out after immersing this glass in water for 1 hour, but the time until the image on the glass became visible clearly was 30 seconds, and the deterioration of hydrophilicity was very slight. In addition, using a traverse tester, the flannel was 19.6 kPa (0.2
A load of kgf / cm ² ) was applied and a test was performed 60 times at a speed of once / second and a stroke of 100 mm, but no scratches were generated on the surface.

[Example 19] AZS-A (product number manufactured by Nippon Shokubai Kagaku Co., Ltd.) as a zirconia sol was added to silica sol prepared in the same manner as in Example 9, and the mixing ratio of silica and zirconia was 95: 5 by weight. Mix to give 5,
Further, as sodium sulfonate compound, sodium di (2-ethylhexyl) sulfosuccinate (NIKKOL
OTP-100 Nikko Chemicals Co., Ltd. product name)
In a ratio of 20 parts by weight to 100 parts by weight of a mixture of silica and zirconia, and an 8: 1 mixed solvent of isopropyl alcohol and water so that the solid content concentration is 1.5% by weight. To obtain a coating solution.
This coating liquid was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method, dried and then baked at 200 ° C. for 30 minutes to give a film thickness of about 100 nm. A transparent hydrophilic film was formed.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 20 seconds after spraying water, the water film became thin and uniform, and the image reflected on the glass became very clear. The same evaluation was carried out after immersing this glass in water for 1 hour, but the time until the image on the glass became visible clearly was 40 seconds, and the deterioration of hydrophilicity was very slight. In addition, using a traverse tester, the flannel was 19.6 kPa (0.2
A load of kgf / cm ² ) was applied and a test was performed 60 times at a speed of once / second and a stroke of 100 mm, but no scratches were generated on the surface.

Example 20 To a silica sol prepared in the same manner as in Example 9, sodium di (2-ethylhexyl) sulfosuccinate (NIKKOL OTP-100, trade name, manufactured by Nikko Chemicals Co., Ltd.) was used as a sodium sulfonate compound. Dispersed in a ratio of 20 parts by weight with respect to 100 parts by weight, 8 parts of isopropyl alcohol and water were added so that the solid content concentration becomes 0.3, 0.5, 4, 5, 7% by weight, respectively. It was diluted with the mixed solvent of 1 to obtain a coating liquid. This coating solution was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method, dried and then heated to 200 ° C.
Was baked for 30 minutes to form a hydrophilic film.

The characteristics of the hydrophilic film thus obtained are as follows.
As shown in Table 2, a transparent hydrophilic film having a durability of 0.5, 4,5% by weight was obtained, but a hydrophilic concentration of 0.3% by weight resulted in insufficient hydrophilic performance. , Dilution concentration 7
When the content was wt%, cracks were generated during firing and a transparent hydrophilic film could not be obtained.

[0098]

[Table 2]

Comparative Example 5 Sodium di (2-ethylhexyl) sulfosuccinate (NIKKOL OTP-100 Nikko Chemicals Co., Ltd. as a sodium sulfonate compound was formed on the surface of the glass prepared in the same manner as in Example 9 opposite to the plated surface. IPA with 5% concentration of product name)
The solution was included in a cloth and applied by hand. Then at 150 ℃ 1
Dry for 0 minutes and evaporate the IPA. A sodium sulfonate compound crystallized on the obtained surface and became cloudy in white, and a transparent film was not obtained.

Further, water was sprayed on the surface of the obtained hydrophilic glass, and the image clarity on the glass was observed. About 15 seconds after spraying water, the water film became thin and uniform, and the image on the glass became very clear. However, when this glass was immersed in water for 1 hour and subjected to the same evaluation, the hydrophilicity deteriorated and the adhered water did not form a uniform water film, and the image reflected on the glass looked clear. It didn't happen.

[Comparative Example 6] A liquid superabsorbent polymer stock solution (Sumikagel L-5H, trade name manufactured by Sumitomo Chemical Co., Ltd.) was formed on the surface of the glass prepared in the same manner as in Example 9 opposite to the plated surface. ) Was spin coated at 1000 rpm for 20 seconds. This was heated at 100 ° C. for 1 hour, and the stock solution was post-cured to form a transparent film of a water-insoluble superabsorbent polymer.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 60 seconds after spraying water, the water film became thin and uniform, and the image on the glass became very clear. The same evaluation was performed after immersing this glass in water for 1 hour, but it took 90 seconds until the image on the glass became clear and there was almost no deterioration in hydrophilicity.

However, using a traverse tester, a load of 19.6 kPa (0.2 kgf / cm ² ) was applied to the flannel and a test was performed 60 times at a speed of once / second and a stroke of 100 mm. It was not possible to say that this was a hydrophilic film having sufficient scratch resistance because a lot of very noticeable scratches were generated and partial peeling occurred.

Comparative Example 7 A silica sol prepared in the same manner as in Example 9 was mixed with sodium di (2-ethylhexyl) sulfosuccinate (N) as a sodium sulfonate compound.
IKKOL OTP-100 (trade name, manufactured by Nikko Chemicals Co., Ltd.) is dispersed in a ratio of 3 parts by weight with respect to 100 parts by weight of silica, and further 8 parts of isopropyl alcohol and water are added so that the solid content concentration becomes 2% by weight. It was diluted with the mixed solvent of 1 to obtain a coating liquid. This coating liquid was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method and dried,
Firing was performed at 200 ° C. for 30 minutes to form a transparent hydrophilic film having a film thickness of about 100 nm.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
After spraying water, the time until the water film becomes thin and uniform is about 2
For 40 seconds, it took a long time until the image displayed on the glass became very clear, and sufficient hydrophilicity was not obtained.

Comparative Example 8 A silica sol prepared in the same manner as in Example 9 was mixed with sodium di (2-ethylhexyl) sulfosuccinate (N) as a sodium sulfonate compound.
IKKOL OTP-100 (trade name, manufactured by Nikko Chemicals Co., Ltd.) is dispersed in a ratio of 70 parts by weight to 100 parts by weight of silica, and further 8 parts of isopropyl alcohol and water are added so that the solid content concentration becomes 2% by weight. What was diluted with the mixed solvent of 1 was used as the coating liquid. This coating liquid was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method, dried and then baked at 200 ° C. for 30 minutes to give a film thickness of about 10
A 0 nm hydrophilic film was formed. The film was slightly hazy.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
About 20 seconds after spraying water, the water film became thin and uniform, and the image reflected on the glass became very clear. The same evaluation was carried out after immersing this glass in water for 1 hour, but the time until the image on the glass became visible clearly was 30 seconds, and the deterioration of hydrophilicity was very slight. However, using a traverse tester, the flannel was 19.6 kPa (0.
2kgf / cm ² ) was applied and the test was carried out 60 times at a speed of once / second and a stroke of 100 mm. As a result, many scratches were generated on the surface and it cannot be said that the film has sufficient hardness. there were.

Comparative Example 9 A silica sol prepared in the same manner as in Example 9 was mixed with sodium di (2-ethylhexyl) sulfosuccinate (N) as a sodium sulfonate compound.
IKKOL OTP-100 (trade name, manufactured by Nikko Chemicals Co., Ltd.) is dispersed in a ratio of 20 parts by weight to 100 parts by weight of silica, and further 8 parts of isopropyl alcohol and water are added so that the solid content concentration becomes 2% by weight. What was diluted with the mixed solvent of 1 was used as the coating liquid. This coating solution was applied to the surface of the glass prepared in the same manner as in Example 9 on the side opposite to the plated surface by a flow coating method, dried and then baked at 350 ° C. for 30 minutes to give a film thickness of about 70.
nm film was formed. Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed. Even after 5 minutes from spraying water, a uniform water film was not formed, and it is considered that the sodium sulfonate was decomposed by the baking at the decomposition temperature or higher and the hydrophilicity was not obtained.

[Comparative Example 10] In a silica sol prepared in the same manner as in Example 9, hydroxyethyl methacrylate was dispersed in a ratio of 20 parts by weight to 100 parts by weight of silica, and the solid content concentration was 2% by weight. A coating solution was prepared by diluting it with an 8: 1 mixed solvent of isopropyl alcohol and water. This coating liquid was used in Example 9.
Was coated on the surface of the glass prepared in the same manner as the above with the surface opposite to the plated surface by the flow coating method and dried, and then 200
Firing was performed at 30 ° C. for 30 minutes to form a transparent hydrophilic film having a film thickness of about 0.1 μm.

Water was sprayed on the surface of the hydrophilic glass thus obtained, and the image clarity on the glass was observed.
It takes about 1 time for the water film to become thin and uniform after spraying water.
It took 80 seconds to obtain a clear image on the glass, which was slightly long, and although it was hydrophilic, it was insufficient. Table 3 shows the characteristics of the compositions of Examples 9 to 20 and Comparative Examples 5 to 10 and the performance of the obtained hydrophilic films.

[0111]

[Table 3]

[0112]

EFFECT OF THE INVENTION According to the hydrophilic glass of the present invention, a transparent structure is obtained by dispersing a hydrophilic organic compound such as ester, sulfate or sodium sulfonate compound in a hard metal oxide film. A hydrophilic film is obtained,
It is possible to exert an excellent effect of preventing water droplets from adhering and the effect lasts for a long period of time, and at the same time, to have high scratch resistance.

Claims (8)

[Claims] 1. In a glass having a reflective coating on one surface of a glass substrate, the film thickness is 0.01 to 0.5 μm on the surface opposite to the coating surface of the glass substrate.
At least one selected from the group consisting of fatty acid esters, fatty acid ethers, sulfuric acid esters, phosphoric acid esters, and hydrophilic organic compounds such as sulfates in the metal oxide film. A hydrophilic glass comprising one kind of a hydrophilic film contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of a metal oxide. 2. The hydrophilic organic compound contained in the metal oxide is glycerin fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester or ether, sorbitol ethylene oxide adduct fatty acid ester, higher alcohol oxycarboxylic acid ester, At least one selected from the group consisting of cyanoethylated or carbamoylethylated fatty acid esters of polyhydric alcohols, ethylene oxide adducts of sorbitan higher fatty acid esters, alkyl sulphates, alkylallyl sulphates and alkylamine sulphates. The hydrophilic glass according to claim 1. 3. A hydrophilic film containing a sodium sulfonate compound in an amount of 5 to 50 parts by weight based on 100 parts by weight of a metal oxide is formed on one surface or both surfaces of a glass substrate. Characteristic hydrophilic glass. 4. The hydrophilic glass according to claim 3, wherein the sodium sulfonate compound is at least one compound selected from the following chemical formula 1. Embedded image 5. The metal oxide is SiO ₂ and optionally Z
The hydrophilic glass according to claim 1 or 3, which is a multi-component metal oxide containing at least one selected from the group consisting of rO ₂ , TiO ₂ and Al ₂ O ₃ . 6. The hydrophilic glass according to claim 1 or 3, wherein the surface of the hydrophilic film has fine irregularities. 7. A solution obtained by mixing a sol solution of a metal oxide with a hydrophilic organic compound is applied onto a glass substrate and then heated at a temperature not higher than the decomposition temperature of the organic compound and / or ultraviolet rays. The method for producing hydrophilic glass according to claim 1, wherein the hydrophilic film is formed by polycondensing the metal oxide by irradiating the metal oxide. 8. On a glass substrate, 5 to 5 parts by weight of sodium sulfonate-based compound is added to 100 parts by weight of metal oxide.
For a hydrophilic coating obtained by diluting a composition blended in a proportion of 0 parts by weight with water and / or an organic solvent so that the solid content concentration is in the range of 0.5 to 5% by weight. The method for producing hydrophilic glass according to claim 3, wherein the metal oxide is polycondensed by applying the composition and then heating at a temperature not higher than the decomposition temperature of the sodium sulfonate-based compound.