JP2001348445A - Resin substrate for liquid crystal display, manufacturing method thereof and element for liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate for a liquid crystal display having good adhe sion and a highly preventive property of gas-permeability and an element for a liquid crystal display. SOLUTION: After applying a coating solution containing a silicon compound having an organic functional group represented by the general formula: (R1nSi(R2)4-n (1), wherein R1 is an organic functional group having a methacryloxy group; R2 is one or more hydrolyzable groups selected from an alkoxyl group, an acetoxyl group and chlorine; n is an integer of not more than 3) or the hydrolysis product on a polysulfone resin, a resin substrate suitable for a liquid crystal display coated with silicon dioxide on a primary coat obtained by drying is obtained. Alternatively, after the primary coat is applied with an applying solution containing a plurality of: hydrolizable silicon compounds having a functional group selected from a methacryloxy group, a vinyl group, an allyl group or an amino group; a silicon compound different from each other of their hydrolysis products; and/or their hydrolysis products, the substrate obtained by drying may be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin substrate for a liquid crystal display and a method for manufacturing the same. For more information,
The present invention relates to a resin substrate for liquid crystal display using a polysulfone resin coated with silicon dioxide, and a liquid crystal display element.

[0002]

2. Description of the Related Art In recent years, with the development of information and communication related technologies, demand for lightweight and small-sized information terminals, such as portable telephones and portable personal computers, which are easy to carry has been increasing. For this reason, a resin material that emphasizes lightness has begun to be used instead of conventional glass for a display substrate used for a portable terminal. Further, one of the characteristics of the resin material in a display for a portable terminal is that it has excellent impact resistance as compared with glass. On the other hand, since a transparent conductive film and a color filter are laminated on the display substrate, the resin material has mechanical properties, moisture resistance,
It is necessary to satisfy workability and dimensional stability.

[0003] Polysulfone-based resins are thermoplastic resins having excellent heat resistance, and have recently attracted attention as representatives of so-called engineering plastics.
Among them, amorphous polyethersulfone is a material that has high dimensional stability, heat resistance, creep characteristics, workability, and chemical resistance, and is required for liquid crystal display substrates such as display substrates for portable devices. It is a material that satisfies basic characteristics.

[0004]

However, when a transparent conductive film is directly formed on a polysulfone resin by a vacuum film forming method, a low molecular compound such as a plasticizer contained in the resin material is vaporized as a gas, Good film quality could not be obtained. Further, although polysulfone resin is excellent in moisture resistance, when left under high humidity, warpage due to moisture absorption cannot be completely avoided, and the precise dimensional stability required for liquid crystal displays cannot be satisfied.

Therefore, an object of the present invention is to establish a method for forming a coating layer capable of imparting high gas permeability (including water permeability prevention) on polysulfone resin with good adhesion, and to obtain a good adhesion and high gas permeability. An object of the present invention is to provide a liquid crystal display substrate and a liquid crystal display element having prevention properties.

[0006]

The above object of the present invention can be solved by the following constitution. That is, a primary coating made of an organosilicon compound is applied to a polysulfone resin, and a solution containing hydrosilicofluoric acid in which silicon dioxide is in a supersaturated state is brought into contact with a substrate to form a silicon dioxide on the primary coating. This is a method for producing a resin substrate for a liquid crystal display on which a film is formed.

If the surface of the polysulfone resin is subjected to a hydrophilic treatment before the formation of the primary coating, the adhesion between the resin and the primary coating can be improved.

The primary coating is represented by the following general formula (1): R ¹ _n Si (R ² ) _4-n (1) where R ¹ is an organic functional group having a methacryloxy group, and R ² is One or more hydrolyzable groups selected from an alkoxyl group, an acetoxyl group and chlorine;
n is preferably obtained by applying a coating solution containing a silicon compound having an organic functional group represented by an integer of 3 or less or a hydrolyzate thereof, followed by drying.

Further, as the above-mentioned primary film of the present invention,
Formula (2) R ³ _n Si (R ² ) _4-n (2) Here, R ³ is an organic functional group having a functional group selected from a methacryloxy group, a vinyl group, an allyl group, or an amino group. ² is one or more hydrolyzable groups selected from an alkoxyl group, an acetoxyl group and chlorine;
n is a silicon compound having an organic functional group represented by an integer of 3 or less, or a hydrolyzate thereof, obtained by applying a coating liquid containing a plurality of different silicon compounds or hydrolysates thereof and then drying. Is more desirable.

When the primary coating obtained from a coating solution containing a plurality of silane compounds of the general formula (2) is used as the primary coating of the present invention, only the silane compound of the general formula (1) is used. Properties such as adhesion to polysulfone resin are higher than in the case of using a primary coating obtained from a coating solution.

[0011] The present invention also includes a resin substrate for a liquid crystal display obtained by the above manufacturing method. Further, the present invention includes a liquid crystal display element using the resin substrate for liquid crystal display.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The present invention after hydrophilic treatment polysulfone resin, to form an organic silicon coating, further, which SiO ₂ is immersed in H ₂ SiF ₆ aqueous solution maintained supersaturated S
A coating of iO ₂ is formed.

Further, by interposing an organic silicon film on the surface of the polysulfone resin by the above-mentioned manufacturing method, the adhesion between the polysulfone resin and the SiO ₂ film can be improved. At this time, if the surface of the polysulfone resin is subjected to a hydrophilization treatment and then the SiO ₂ film is formed via the organic silicon film, the adhesion between the polysulfone resin and the SiO ₂ film can be further reliably increased.

The polysulfone resin used as the substrate is
Polyallyl sulfone, polyether sulfone, or the like can be used. Among them, polyethersulfone is more preferable because it has excellent basic properties required for a liquid crystal display substrate.

The hydrophilic treatment of the substrate surface of the polysulfone resin may be performed by any method as long as the surface of the resin substrate can be made hydrophilic. For example, a corona discharge treatment, a plasma treatment, a UV ozone treatment, an ozone water cleaning, etc. An oxidizing treatment method is used. Without this step, a good film cannot be formed due to poor adhesion, although a silicon dioxide film can be formed. The surface of the polysulfone resin can be hydrophilized by a treatment such as UV ozone washing, corona discharge treatment, plasma treatment by high-frequency plasma discharge, or ozone water washing without deteriorating the surface of the polysulfone resin. In addition to these treatments, in addition to the oxidizing action of the polysulfone resin surface,
It also has the function of removing surface dirt and oil. Next, a specific example of the hydrophilic treatment will be described.

In the UV ozone cleaning, the distance between the polysulfone resin substrate and the UV lamp is set to 20 to 50 in an atmosphere containing oxygen.
Irradiation is performed at 20 mW / cm ² for 1 to 20 minutes. At this time, the polysulfone resin substrate is 30
When heated to 100 ° C., the hydrophilic treatment can be performed quickly.

In the corona discharge, the distance between the electrode and the polysulfone resin substrate is maintained at a distance of 0.5 to 8 mm, and
A corona discharge is generated between the electrode and the substrate surface while the substrate is moved under the electrode at a speed of mm / sec. Discharge cycle 15
It is performed in air by applying a voltage of 10 kHz to 30 kHz.

The plasma treatment using high-frequency plasma discharge is a method in which a glow discharge is generated between an electrode and a substrate in a reduced-pressure oxygen atmosphere to hydrophilize the surface of the polysulfone resin.

Ozone water cleaning is a few ppm with an oxidizing action.
This is a method in which the surface is made hydrophilic by immersing the substrate for several minutes in water in which about ozone is dissolved.

By performing these treatments, the resin surface is made hydrophilic. Looking at the elemental composition of the surface by XPS, the amount of oxygen is larger than before the hydrophilization treatment, and the oxygen is a hydroxyl group,
It is introduced only in the vicinity of the resin surface in the form of sulfonic acid groups. By these functional groups become the binding site with the coating,
A film can be formed. When a good film can be formed, the contact angle of the water droplet is approximately 65 degrees or less.

The thickness of the primary coating film obtained by applying a coating solution containing a silicon compound having an organic functional group or a hydrolyzate thereof is preferably 2 to 50 nm.
If the thickness of the primary coating is less than 2 nm, problems tend to occur in the uniformity and adhesion of the silicon dioxide coating, which is not preferable. On the other hand, when the thickness of the primary coating is larger than 50 nm, there is no problem when the polysulfone resin substrate is flat, but in the case of a substrate having a complicated shape, the coating property of the surface may be deteriorated. Again, it is not preferable.

The thickness of the primary coating is determined by the concentration of the organic silicon compound contained in the coating solution and the coating conditions, and it is necessary to select them appropriately. As a solvent of the coating solution, water may be used in addition to an organic solvent such as alcohol.
The method for applying the primary coating may be any of dipping, spraying, and flow coating.

The silicon compound of the general formula (1) is R ¹ _n Si (R ² ) _4-n (1) where R ¹ is an organic functional group having a methacryloxy group, and R ² is an alkoxyl group or an acetoxyl group. And one or more hydrolyzable groups selected from chlorine and
n is represented by an integer of 3 or less. Specific examples of the silicon compound of the general formula (1) are as follows.

3-methacryloxypropylmethyldichlorosilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethylmethoxyethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylacetoxysilane, 3-methacryloxypropylmethyldiacetoxysilane, 3-methacryloxypropylmethylmethoxyacetoxysilane, 3-methacryloxypropylmethylethoxyacetoxysilane, 3-methacryloxypropylmethoxydiethoxysilane, 3-methacryloxypropylmethoxydiacetoxysilane,

3-methacryloxypropylmethoxyethoxyacetoxysilane, 3-methacryloxypropyldimethoxyacetoxysilane, 3-methacryloxypropyldimethoxyethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylethoxydiacetoxysilane, 3-methacryloxypropyldiethoxyacetoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriacetoxysilane, 3-methacryloxypropyltrichlorosilane

2-methacryloxyethylmethyldichlorosilane, 2-methacryloxyethyltrichlorosilane,
2-methacryloxyethylmethyldimethoxysilane, 2
-Methacryloxyethyltrimethoxysilane, 2-methacryloxyethylmethyldiethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxyethylmethyldiacetoxysilane, 2-methacryloxyethylethyldiacetoxysilane,

2-methacryloxyethyltriacetoxysilane, 2-methacryloxyethylmethylmethoxyethoxysilane, 2-methacryloxyethyldimethylacetoxysilane, 2-methacryloxyethylmethylmethoxyacetoxysilane, 2-methacryloxyethylmethylethoxyacetoxysilane 2-methacryloxyethylmethoxydiethoxysilane, 2-methacryloxyethylmethoxydiacetoxysilane, 2-methacryloxyethylmethoxyethoxyacetoxysilane, 2-methacryloxyethyldimethoxyacetoxysilane, 2-methacryloxyethyldimethoxyethoxysilane, 2 -Methacryloxyethylethoxydiacetoxysilane, 2-methacryloxyethyldiethoxyacetoxysilane,

Methacryloxymethylmethyldichlorosilane, methacryloxymethyltrichlorosilane, methacryloxymethylmethyldimethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethylmethyldiethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyldimethoxysilane , Methacryloxymethyldiethoxysilane, methacryloxymethylmethyldiacetoxysilane, methacryloxymethylmethylmethoxyacetoxysilane,

Methacryloxymethyldimethoxyacetoxysilane, methacryloxymethylmethoxyethoxyacetoxysilane, methacryloxymethyldiethoxyacetoxysilane, methacryloxymethylmethylmethoxyethoxysilane, methacryloxymethyldimethylacetoxysilane, methacryloxymethylmethylethoxyacetoxysilane, methacryl Roxymethylmethoxydiacetoxysilane, methacryloxymethyldimethoxyethoxysilane, methacryloxymethylethoxydiacetoxysilane, methacryloxymethyltriacetoxysilane,

2-methacryloxyethylmethylmethoxyacetoxysilane, 2-methacryloxyethyldimethoxyacetoxysilane, 2-methacryloxyethylmethylethoxyacetoxysilane, 2-methacryloxyethyldiethoxyacetoxysilane, 2-methacryloxyethylmethyldichlorosilane , 2-methacryloxyethylmethyldimethoxysilane,

2-methacryloxyethylmethylmethoxyethoxysilane, 2-methacryloxyethylmethyldiethoxysilane, 2-methacryloxyethyldimethylacetoxysilane, 2-methacryloxyethylmethyldiacetoxysilane, 2-methacryloxyethylmethoxydiethoxy Silane, 2-methacryloxyethylmethoxydiacetoxysilane, 2-methacryloxyethylmethoxyethoxyacetoxysilane, 2-methacryloxyethyldimethoxyacetoxysilane,

2-methacryloxyethyldimethoxyethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethylethoxydiacetoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxyethyltriacetoxysilane,
2-methacryloxyethyltrichlorosilane

An ester group is present in the organic silicon-containing coating obtained from the silicon compound in which R ¹ of the compound of the general formula (1) is a methacryloxypropyl group or a hydrolysis product thereof. When this ester group is contained in the organic silicon-containing film, the adhesion is improved, although the reason is not clear, when the silicon dioxide film is deposited on the film from a hydrosilicofluoric acid solution.

The silicon compound represented by the general formula (2) is R ³ _n Si (R ² ) _4-n (2) where R ³ is a functional group selected from a methacryloxy group, a vinyl group, an allyl group and an amino group. Wherein R ₂ is one or more hydrolyzable groups selected from an alkoxyl group, an acetoxyl group and chlorine;
n is represented by an integer of 3 or less. Specific examples of the silicon compound of the general formula (2) are as follows in addition to the examples of the general formula (1) described above.

Vinylmethyldichlorosilane, vinyltrichlorosilane, vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinylmethyldiethoxysilane,
Vinyltriethoxysilane, vinylmethyldiacetoxysilane, vinyltriacetoxysilane,

Allylmethyldichlorosilane, allyltrichlorosilane, allylmethyldimethoxysilane, allyltrimethoxysilane, allylmethyldiethoxysilane,
Allyltriethoxysilane, allylmethyldiacetoxysilane, allyltriacetoxysilane,

3- (N-allylamino) propylmethyldichlorosilane, 3- (N-allylamino) propyltrichlorosilane, 3- (N-allylamino) propylmethyldimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, 3- (N-allylamino) propylmethyldiethoxysilane, 3- (N-allylamino) propyltriethoxysilane, 3- (N-allylamino) propylmethyldiacetoxysilane, 3- (N-
Allylamino) propyltriacetoxysilane,

3-aminopropylmethyldichlorosilane, 3-aminopropyltrichlorosilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane Silane,
3-aminopropylmethyldiacetoxysilane, 3-aminopropyltriacetoxysilane,

N- (2-aminoethyl) -3-aminopropylmethyldichlorosilane, N- (2-aminoethyl) -3-aminopropylpyrrochlorosilane, N- (2
-Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl)-
3-aminopropylmethyldiethoxysilane, N- (2
-Aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiacetoxysilane, N- (2-aminoethyl)
-3-aminopropyltriacetoxysilane

R ^{3 in the} general formula (2) is a silicon compound having an amino group, and the primary coating obtained from the silicon compound has a sulfonic acid group or a hydroxyl group on the outermost surface of the polysulfone resin subjected to the hydrophilic treatment. And a large number of amino groups exhibiting strong interaction with each other, the adhesion at the interface between the resin substrate and the primary coating is improved.

For example, even in the case of a primary coating containing only a silicon compound having a methacryloxy group in R ¹ of the general formula (1), a silicon dioxide coating can be formed uniformly thereon. However, in order to further improve the adhesion of the coating, at least two different compounds of the general formula (2) are used in the present invention.
Primary coatings formed from more than one species can be used.

In the first coating film obtained by using the silicon compound in which R ^{3 in the} general formula (2) contains only a silicon compound having a functional group having an amino group, the silicon compound having the amino group is hydrophilic. When the silicon dioxide film is formed by contacting a hydrosilicic acid solution containing silicon dioxide in a supersaturated state later, a silicon compound having an amino group is eluted, and the silicon dioxide film is uniformly formed. Inhibits the membrane.

Therefore, as a raw material for the primary coating, a reactive group having low hydrophilicity such as a methacryloxy group, a vinyl group, or an allyl group, in addition to the silicon compound in which R ^{3 in the} general formula (2) contains an amino group, is used. combining silicon compound containing as R ^3, formation of the silicon dioxide film after are performed uniformly. The reason why the formation of the silicon dioxide film is uniform is not clear, but it is presumed to be because it helps to orient organic functional groups to the resin interface and silanol groups to the silicon dioxide film in the film. ing.

The silicon compound containing an amino group is desirably in the range of 0.01 to 70% by weight of the total silicon compound contained in the coating solution. The amount of the silicon compound containing an amino group is 0.
If the amount is less than 01% by weight, the effect of improving the adhesion cannot be expected. On the other hand, if it is more than 70% by weight, it is not preferable because a silicon dioxide film cannot be formed uniformly.

However, it is not always necessary to use a compound containing a silicon compound containing an amino group as R ^{3 in the} general formula (2), and it is not necessary to use any one of the above methacryloxy group, vinyl group and allyl group. They may be used in combination of compounds. In this case, the adhesion to the polysulfone resin is slightly inferior to the case where a silicon compound in which R ^{3 in the} general formula (2) contains an amino group is used as one of the components.

The polysulfone resin substrate on which the primary coating has been formed is brought into contact with a hydrosilicofluoric acid solution containing silicon dioxide in a supersaturated state to form a silicon dioxide coating on the primary coating. Silicon hydrofluoric acid in a supersaturated state of silicon dioxide (H
₂ SiF ₆ ) solution (hereinafter sometimes abbreviated as “treatment solution”) is prepared by dissolving silicon dioxide (silica gel, airgel, silica glass, and other substances containing silicon dioxide) in a hydrofluoric acid solution. Water or reagents (boric acid,
Aluminum chloride, metallic aluminum, etc.) or a method in which silicon dioxide is supersaturated by means such as increasing the temperature of the processing solution is used.

In the present invention, the concentration of hydrosilicofluoric acid in the treatment liquid to be brought into contact with the substrate of the polysulfone resin molded article having the primary coating is preferably from 1 to 4 mol / l, particularly preferably from 3 mol / l. Saturated silicon dioxide in a concentrated aqueous solution of hydrosilicofluoric acid, and then diluted with water to a concentration of 1 to 4 mol / liter is preferable because the film formation speed is high and the film can be formed efficiently.

In addition, (a) even when the treatment liquid is in contact with the resin substrate, an aqueous solution of an additive such as boric acid or aluminum chloride is continuously added and mixed. The metal such as aluminum is dissolved and mixed. (B) a processing liquid whose supersaturation degree is constantly maintained by means such as temporarily cooling the temperature to saturate the silicon dioxide and then raising the temperature again. % Or more of the treatment liquid is preferably a treatment liquid that is filtered through a filter and used in circulation.

Here, at the time of contact with the resin substrate,
It is preferable to continuously add and mix an aqueous solution such as boric acid or to dissolve and mix a metal such as aluminum in order to improve the film formation speed. In the case of boric acid, the addition amount is 5 × 10 5 per mol of hydrosilicofluoric acid in the processing solution.
^-4 mol / hr to 1.0 × 10 ^-3 mol / hr is preferable, and when dissolving aluminum metal, the amount of the dissolution is based on 1 mol of hydrosilicofluoric acid in the treatment liquid. The range is preferably from 1 × 10 ⁻³ mol / hr to 4 × 10 ⁻³ mol / hr.

It is effective to circulate a processing solution having a hydrosilicofluoric acid concentration of 3% or more to continuously obtain a uniform film, and it is effective to filter the processing solution with a filter. It is preferable to obtain an uncoated film.

When the treatment liquid is put into the immersion tank and brought into contact with the resin substrate, it is necessary to make the treatment liquid flow in a laminar flow on the surface of the resin substrate during immersion. It is effective to get.

The silicon dioxide film obtained by such a deposition method contains adsorbed water and silanol groups. To remove these, it is necessary to subject the film to a heat treatment using a high frequency or the like. Is preferred.

In this way, a silicon dioxide film having excellent adhesion can be formed on the surface of the polysulfone resin. Therefore, the trace gas (plasticizer, H ₂ O, etc.) contained in the resin can be formed by the silicon dioxide film having high adhesion. ) And the release of the trace gas from the surface of the polysulfone resin coated with silicon dioxide. Further, the trace gas in the use atmosphere can be prevented from being absorbed into the resin.

That is, according to the present invention, a silicon dioxide film having excellent adhesion can be formed on the surface of the polysulfone resin, so that a resin substrate for liquid crystal displays and the like having excellent gas permeation prevention properties can be obtained. In addition, the gas permeation prevention property includes the water permeation prevention property. Thus, according to the present invention, the mechanical characteristics of the polysulfone resin, taking advantage of excellent features such as heat resistance,
It can be used for a liquid crystal display resin substrate.

[0055]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 A polyether sulfone substrate manufactured by ICI (size:
A variable voltage of up to about 14000 volts and a frequency of about 15 kHz using a corona discharge surface reformer “Corona Master” PS-1M manufactured by Shinko Electric Instrumentation Co., Ltd. at 100 mm × 150 mm × 0.4 mmt). The corona discharge treatment was performed at a speed of 5 mm per second so that the contact angle of water on the surface of the polysulfone substrate was 33 degrees.

Next, a 1% solution of 3-methacryloxypropyltrimethoxysilane in ethyl alcohol was prepared.
Further, an amount of water necessary for hydrolyzing the methoxy group was added, and the mixture was sufficiently stirred to obtain a coating solution. The coating liquid was applied to the resin substrate subjected to the corona discharge treatment by a dipping method, and was naturally dried to form a primary coating having a thickness of 10 nm.

Thereafter, the resin substrate with the primary coating was immersed in a 2.5 mol / liter hydrosilicofluoric acid (H ₂ SiF ₆ ) solution in which silicon dioxide was in a supersaturated state at a liquid temperature of 30 ° C. The immersion time was a time required for obtaining a silicon dioxide film having a thickness of 100 nm. Thereafter, the resin substrate was taken out, washed with water, and then dried in an oven at 50 ° C. for 1 hour. The silicon dioxide film formed on the resin substrate was uniform and had no external defects such as unevenness.

Next, a cellophane tape manufactured by Nichiban Co., Ltd. was adhered on the silicon dioxide film, and then vigorously peeled off, immediately after film formation (initial stage) and in a moisture resistance test (40 ° C.,
The adhesion of the coating after 95% RH and 200 h) was evaluated.
There was no problem in the initial adhesion, only partial peeling of the coating was observed after the moisture resistance test.

Further, as a water permeability test of a silicon dioxide film formed on a resin substrate, the water permeability was determined according to JIS as follows.
It measured by the moisture-permeable cup method according to Z-0208.

First, a predetermined amount of a desiccant (anhydrous calcium chloride, anhydrous silica gel) is put into a cup, the opening of the cup is covered with a polyether sulfone substrate coated with silicon dioxide, and the opening is made of a water-impermeable material. The gap between the part and the substrate is sealed. The sample thus obtained is placed in a high-temperature and high-humidity tank at 40 ° C. and a humidity of 90% and held for a predetermined time. After a lapse of a predetermined time, the sample is taken out, the weight of the desiccant in the cup is measured, and the weight increase is regarded as the amount of moisture permeating the substrate, and is defined as the amount of water per unit time and per unit area. When the amount of water permeation is less than ² g / m ² · day ◎, when the amount of water permeation is 10 g /
Less than m ² · day was rated as Δ, and water permeability of 10 g / m ² · day or more was rated as ×.

The water permeability test of the substrates obtained in Examples 1 to 23 shown below was ◎, the water permeability test of the substrates obtained in Examples 24 to 26 was Δ, and the water permeability test was obtained in Comparative Examples 1 to 11. The substrate had a water permeability test of ×.

Example 2 Using a UV lamp (product number: SGL-18W18S-SA1) manufactured by Samco International Laboratories Co., Ltd. on the polyethersulfone substrate manufactured by ICI (company) used in Example 1, the UV immediately below the lamp was used. When UV irradiation is performed on the substrate so that the illuminance becomes 20 mW / cm ² , ozone is generated on the substrate, and oil and the like on the substrate surface are decomposed. UV
The ozone cleaning treatment was performed for 15 minutes so that the contact angle of water on the resin substrate surface was 6 degrees. Furthermore, a primary coating and a silicon dioxide coating were formed in the same manner as in Example 1, and the adhesion of the coating was evaluated in the same manner as in Example 1. As a result, peeling of the coating was found after the moisture resistance test. There was no problem in the initial adhesion just by being performed.

Example 3 A polysulfone substrate surface was subjected to a hydrophilic treatment in the same manner as in Example 2 except that the UV ozone cleaning treatment time was set to 5 minutes (the contact angle of water on the substrate surface was 40 degrees). Primary coating (thickness: 10 nm) and silicon dioxide coating (thickness: 100 n)
m) was formed, and the adhesion of the coating was evaluated in the same manner as in Example 1. As a result, there was no problem in the initial adhesion because only partial peeling of the coating was observed after the moisture resistance test.

Example 4 A polysulfone substrate surface was subjected to a hydrophilic treatment in the same manner as in Example 2 except that the UV ozone cleaning treatment time was set to 2 minutes (the contact angle of water on the substrate surface was 53 degrees). Primary coating (thickness: 10 nm) and silicon dioxide coating (thickness: 100 n)
m) was formed, and the adhesion of the coating was evaluated in the same manner as in Example 1. As a result, only a part of the coating was peeled off.

Example 5 A polysulfone substrate surface was hydrophilized in the same manner as in Example 2 except that the UV ozone cleaning treatment time was 30 minutes (the contact angle of water on the substrate surface was 5 degrees). Primary coating (2 nm thick) and silicon dioxide coating (100 nm thick)
Was formed, and the adhesion of the coating was evaluated in the same manner as in Example 1. As a result, there was no problem in the initial adhesion because only partial peeling of the coating was observed after the moisture resistance test.

Example 6 A polysulfone substrate surface was hydrophilized in the same manner as in Example 2 except that the UV ozone cleaning treatment time was 30 minutes (the contact angle of water on the substrate surface was 5 degrees). Primary coating (50 nm thickness) and silicon dioxide coating (20 nm thickness)
Was formed, and the adhesion of the coating was evaluated in the same manner as in Example 1. As a result, there was no problem in the initial adhesion because only partial peeling of the coating was observed after the moisture resistance test.

Example 7 The UV ozone cleaning treatment time was set to 5 minutes (the contact angle of water on the substrate surface was 40 degrees), and 3-methacryloxypropyltriethoxysilane was used instead of 3-methacryloxypropyltrimethoxysilane. After the surface of the polysulfone substrate was hydrophilized in the same manner as in Example 2 except that it was used, a primary coating (thickness: 10 nm) and a silicon dioxide coating (thickness: 100 nm) were formed. When the adhesion of the coating was evaluated by the same method, there was no problem in the initial adhesion only after the coating was partially peeled off after the moisture resistance test.

Example 8 The UV ozone cleaning treatment time was set to 5 minutes (the contact angle of water on the substrate surface was 40 degrees), and 3-methacryloxypropylmethyldimethoxysilane was used instead of 3-methacryloxypropyltrimethoxysilane. After the surface of the polysulfone substrate was subjected to a hydrophilization treatment in the same manner as in Example 2 except that it was used, a primary coating (thickness: 5 nm) and a silicon dioxide coating (thickness: 100 nm) were formed. When the adhesion of the coating was evaluated by the same method, there was no problem in the initial adhesion only after the coating was partially peeled off after the moisture resistance test.

Example 9 Using a plasma reactor model PR-501A manufactured by Yamato Scientific Co., Ltd. on the polyethersulfone substrate manufactured by ICI (company) used in Example 1, a high frequency of 13.56 MHz (output: 100 to 200 W) was used. , Gas used O ₂ (flow rate 100
(ml / min) for 2 minutes.
The contact angle of water on the surface of the resin substrate was set to 13 degrees.
In the same manner as in Example 1, a primary coating made of 3-methacryloxypropyltrimethoxysilane and supersaturated Si
When a silicon dioxide film obtained using an H ₂ SiF ₆ solution containing O ₂ was formed and the adhesion of the film was evaluated in the same manner as in Example 1, partial peeling of the film was observed after the moisture resistance test. There was no problem with the initial adhesion.

Example 10 0.2% by weight of 3-aminopropyltrimethoxysilane
Then, an ethanol solution containing 1.0% by weight of vinyltriethoxysilane and vinyltriethoxysilane was prepared, and an amount of water necessary for hydrolyzing the hydrolyzable group was further added thereto, followed by sufficient stirring to obtain a coating solution. After the surface of the polysulfone resin substrate was hydrophilized in the same manner as in Example 1 (water droplet contact angle was 33 °), a 10 nm-thick primary film was formed in the same manner as in Example 1 using the above coating solution. Formed. Thereafter, a silicon dioxide film (thickness: 100 nm) was formed in the same manner as in Example 1, and the adhesion of the film was evaluated in the same manner as in Example 1. As a result, no peeling of the film occurred even after the moisture resistance test. Did not.

Example 11 The surface of a polysulfone resin substrate was subjected to a hydrophilic treatment (water droplet contact angle: 33 °) in the same manner as in Example 1 except that the corona discharge treatment speed was changed to 1 mm / sec. Using the liquid, a primary coating (thickness: 10 nm) was formed in the same manner as in Example 1, and then a silicon dioxide coating (thickness: 100 nm) was formed in the same manner as in Example 1. When the adhesion of the coating was evaluated in the same manner as in 1,
No peeling of the film occurred even after the moisture resistance test.

Example 12 A polysulfone resin substrate surface was hydrophilized (water droplet contact angle was 33 °) in the same manner as in Example 1 except that the corona discharge treatment speed was changed to 10 mm / sec. Using the liquid, a primary film (thickness: 10 nm) was formed in the same manner as in Example 1, and then a silicon dioxide film (thickness: 100 nm) was formed in the same manner as in Example 1. When the adhesion of the coating was evaluated in the same manner as
No peeling of the film occurred even after the moisture resistance test.

Example 13 A polysulfone resin substrate surface was subjected to a hydrophilic treatment using a plasma processing apparatus in the same manner as in Example 9 (water droplet contact angle: 13 °), and the coating liquid of Example 10 was used. First, a primary film (thickness: 10 nm) was formed in the same manner as in Example 1. Thereafter, a silicon dioxide film (thickness: 10 nm) was formed in the same manner as in Example 1.
0 nm), and the adhesion of the coating was evaluated in the same manner as in Example 1. As a result, no peeling of the coating occurred even after the moisture resistance test.

Example 14 A polysulfone resin substrate surface was subjected to hydrophilic treatment using a UV lamp in the same manner as in Example 2 (water droplet contact angle was 6
Degree), a primary film (thickness: 10 nm) was formed using the coating solution of Example 10 in the same manner as in Example 1, and then a silicon dioxide film (thickness: 100 nm) was formed in the same manner as in Example 1.
Was formed, and the adhesion of the film was evaluated in the same manner as in Example 1. As a result, no peeling of the film occurred even after the moisture resistance test.

Example 15 The surface of a polysulfone resin substrate was hydrophilized using a UV lamp (water droplet contact angle: 40 degrees) in the same manner as in Example 2 except that the treatment time was changed to 5 minutes. A primary coating (thickness: 10 nm) was formed in the same manner as in Example 1 using the coating solution of Example 1, and then a silicon dioxide coating (thickness: 100 nm) was formed in the same manner as in Example 1, and further performed. When the adhesion of the coating was evaluated in the same manner as in Example 1, no peeling of the coating occurred even after the moisture resistance test.

Example 16 3-methacryloxypropyltrimethoxysilane was added to 0.1 g
8% by weight and 3-aminopropyltrimethoxysilane in 0.1%.
An ethanol solution containing 2% by weight was prepared, and an amount of water necessary for hydrolyzing the hydrolyzable group was further added, followed by sufficient stirring to obtain a coating solution. After the surface of the polysulfone resin substrate was hydrophilized in the same manner as in Example 1 (water droplet contact angle was 33 °), a 10 nm-thick primary film was formed in the same manner as in Example 1 using the above coating solution. Formed. Then, a silicon dioxide film (100 nm thick) is formed in the same manner as in Example 1.
Was formed, and the adhesion of the coating film was evaluated in the same manner as in Example 1. Although the haze ratio increased after the moisture resistance test, no peeling of the coating occurred.

Example 17 An ethanol solution containing 0.1% by weight of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and 1.0% by weight of vinyltrimethoxysilane was prepared. An amount of water necessary for hydrolyzing the groups was added and sufficiently stirred to obtain a coating solution. After the surface of the polysulfone resin substrate was hydrophilized in the same manner as in Example 1 (water droplet contact angle was 33 °), a 10 nm-thick primary film was formed in the same manner as in Example 1 using the above coating solution. Formed. Thereafter, a silicon dioxide film (film thickness 1) was formed in the same manner as in Example 1.
00 nm), and the adhesion of the coating was evaluated in the same manner as in Example 1. As a result, no peeling of the coating occurred even after the moisture resistance test.

Example 18 0.3% by weight of 3-aminopropyltriethoxysilane
And an ethanol solution containing 0.7% by weight of 3- (N-allylamino) propyltrimethoxysilane and further adding water necessary for hydrolyzing the hydrolyzable groups, and sufficiently stirring to apply. Liquid. After the surface of the polysulfone resin substrate was hydrophilized in the same manner as in Example 1 (water droplet contact angle was 33 °), a 10 nm-thick primary film was formed in the same manner as in Example 1 using the above coating solution. Formed. Thereafter, a silicon dioxide film (film thickness 1) was formed in the same manner as in Example 1.
00 nm), and the adhesion of the coating was evaluated in the same manner as in Example 1. As a result, no peeling of the coating occurred even after the moisture resistance test.

Example 19 0.7% by weight of 3-aminopropyltriethoxysilane
A-10 (mixed alcohol, manufactured by Ueno Chemical Co., Ltd.) solution containing 0.3% by weight of vinyltriethoxysilane and vinyltriethoxysilane, and an amount required to hydrolyze the hydrolyzable group. Water was added and the mixture was sufficiently stirred to obtain a coating solution. After hydrophilizing the surface of the polysulfone resin substrate in the same manner as in Example 1 (the contact angle of the water droplet is 33 degrees), a thickness of 10 n was obtained in the same manner as in Example 1 by using the above coating solution.
m of primary coatings were formed. Thereafter, a silicon dioxide film (thickness: 100 nm) was formed in the same manner as in Example 1, and the adhesion of the film was evaluated in the same manner as in Example 1. As a result, no peeling of the film occurred even after the moisture resistance test. Did not.

Example 20 Fine Eter A-10 (mixed alcohol manufactured by Ueno Chemical Co., Ltd.) solution containing 0.04% by weight of 3-aminopropyltriethoxysilane and 0.36% by weight of vinyltriethoxysilane Was prepared, water was added in an amount necessary for hydrolyzing the hydrolyzable groups, and the mixture was sufficiently stirred to obtain a coating solution. After hydrophilizing the surface of the polysulfone resin substrate in the same manner as in Example 1 (water droplet contact angle is 33
Degree), a primary film having a thickness of 10 nm was formed in the same manner as in Example 1 using the above coating solution. Then, Example 1
A silicon dioxide film (film thickness: 100 nm) was formed in the same manner as described above, and the adhesion of the film was evaluated in the same manner as in Example 1. As a result, no peeling of the film occurred even after the moisture resistance test.

Example 21 Fine Eter A-10 (a mixed alcohol manufactured by Ueno Chemical Co., Ltd.) solution containing 0.01% by weight of 3-aminopropyltriethoxysilane and 1.0% by weight of vinyltriethoxysilane Was prepared, water was added in an amount necessary for hydrolyzing the hydrolyzable groups, and the mixture was sufficiently stirred to obtain a coating solution. After hydrophilizing the surface of the polysulfone resin substrate in the same manner as in Example 1 (water droplet contact angle is 33 degrees),
Using the above coating solution, a thickness of 10 was obtained in the same manner as in Example 1.
nm primary coating was formed. Thereafter, a silicon dioxide film (film thickness 100 nm) is formed in the same manner as in Example 1,
Further, when the adhesion of the coating was evaluated in the same manner as in Example 1, no peeling of the coating occurred even after the moisture resistance test.

Example 22 3-aminopropyltriethoxysilane was added in an amount of 1.0% by weight.
A-10 (mixed alcohol manufactured by Ueno Chemical Co., Ltd.) solution containing 1.0% by weight of vinyltriethoxysilane and vinyltriethoxysilane, and an amount of the solution necessary for hydrolyzing the hydrolyzable group is further prepared. Water was added and the mixture was sufficiently stirred to obtain a coating solution. After hydrophilizing the surface of the polysulfone resin substrate in the same manner as in Example 1 (the contact angle of the water droplet is 33 degrees), a thickness of 10 n was obtained in the same manner as in Example 1 by using the above coating solution.
m of primary coatings were formed. Thereafter, a silicon dioxide film (thickness: 100 nm) was formed in the same manner as in Example 1, and the adhesion of the film was evaluated in the same manner as in Example 1. As a result, no peeling of the film occurred even after the moisture resistance test. Did not.

Example 23 3-aminopropyltriethoxysilane was added to 0.0002
An ethanol solution containing 1.0% by weight of vinyltriethoxysilane and 1.0% by weight of vinyltriethoxysilane was prepared, and an amount of water necessary for hydrolyzing the hydrolyzable group was added thereto. After hydrophilizing the surface of the polysulfone resin substrate in the same manner as in Example 1 (the contact angle of the water droplet is 33 degrees), a thickness of 10 n was obtained in the same manner as in Example 1 by using the above coating solution.
m of primary coatings were formed. Thereafter, a silicon dioxide film (thickness: 100 nm) was formed in the same manner as in Example 1, and the adhesion of the film was evaluated in the same manner as in Example 1. As a result, no peeling of the film occurred even after the moisture resistance test. Did not.

Example 24 0.2% by weight of 3-aminopropyltriethoxysilane
Then, an ethanol solution containing 1.0% by weight of vinyltriethoxysilane and vinyltriethoxysilane was prepared, and an amount of water necessary for hydrolyzing the hydrolyzable group was added thereto, followed by sufficient stirring to obtain a coating solution. After the surface of the polysulfone resin substrate was hydrophilized in the same manner as in Example 1 except that the corona discharge treatment speed was set to 100 mm / sec (water droplet contact angle was 58 degrees), the same procedure as in Example 1 was performed using the above coating solution. A primary film having a thickness of 10 nm was formed in the same manner. Thereafter, a silicon dioxide film (film thickness 50 to 100 nm, with film thickness unevenness) was formed by the same method as in Example 1, and the adhesion of the film was evaluated by the same method as in Example 1. After the moisture resistance test, No peeling of the film occurred.

Example 25 3-Methacryloxypropyltrimethoxysilane was added to 0.1%.
An ethanol solution containing 4% by weight and 0.4% by weight of vinyltriethoxysilane was prepared, and an amount of water necessary for hydrolyzing the hydrolyzable group was added thereto, followed by sufficient stirring to obtain a coating solution. After hydrophilizing the surface of the polysulfone resin substrate in the same manner as in Example 1 (water droplet contact angle is 33 degrees),
Using the above coating solution, a thickness of 10 was obtained in the same manner as in Example 1.
nm primary coating was formed. Thereafter, a silicon dioxide film (film thickness 50 to 100 nm, with film thickness unevenness) was formed by the same method as in Example 1, and the adhesion of the film was evaluated by the same method as in Example 1. After the moisture resistance test, There was no problem in the initial adhesion, only partial peeling of the coating was observed.

Example 26 0.4% by weight of 3-aminopropyltrimethoxysilane
An ethanol solution containing 0.04% by weight of vinyltriethoxysilane and vinyltriethoxysilane was prepared, and water required for hydrolyzing the hydrolyzable groups was further added, followed by sufficient stirring to obtain a coating solution. After the surface of the polysulfone resin substrate was hydrophilized in the same manner as in Example 1 (water droplet contact angle was 33 °), a 10 nm-thick primary film was formed in the same manner as in Example 1 using the above coating solution. Formed. Thereafter, a silicon dioxide film (film thickness 50 to 100 nm, with film thickness unevenness) was formed by the same method as in Example 1, and the adhesion of the film was evaluated by the same method as in Example 1. After the moisture resistance test, No peeling of the film occurred.

Comparative Example 1 A polyethersulfone substrate (size: ICI)
(100 mm × 150 mm × 0.4 mmt), using the apparatus used in Example 1, a corona discharge treatment at a variable voltage of up to about 14000 volts and a frequency of about 15 kHz was performed at a rate of 5 mm per second, and the surface of the polysulfone substrate was The contact angle of water was set to 40 degrees. Next, a 1% ethyl alcohol solution of 3-glycidoxypropyltrimethoxysilane was prepared, and an amount of water necessary for hydrolyzing the methoxy group was further added, followed by sufficient stirring to obtain a coating solution. On the resin substrate that has been subjected to corona discharge treatment, the coating solution is applied by a dipping method, and naturally dried,
A primary coating having a thickness of 10 nm was formed. Thereafter, an attempt was made to form a silicon dioxide film on the resin substrate by the same method as in Example 1 using a H ₂ SiF ₆ solution containing supersaturated SiO ₂ , but no silicon dioxide film could be formed.

Comparative Example 2 The surface of a polysulfone substrate was hydrophilized in the same manner as in Example 1 except that 3-aminopropyltrimethoxysilane was used instead of 3-methacryloxypropyltrimethoxysilane in Example 1. After (contact angle 4
After forming the primary coating (thickness: 10 nm) at 0 °), an attempt was made to form a silicon dioxide coating, but no silicon dioxide coating was obtained.

Comparative Example 3 The same procedure as in Example 1 was carried out except that the surface of the polysulfone substrate was subjected to a hydrophilic treatment (contact angle: 40 °) and the primary film was not formed. An attempt was made to form a silicon dioxide film on a polysulfone substrate by the method, but no silicon dioxide film was obtained.

Comparative Example 4 A primary coating was applied to the surface of the polysulfone substrate in the same manner as in Example 1 except that the hydrophilic treatment by corona discharge in Example 1 was not performed (the contact angle of pure water on the resin substrate surface was 90 degrees). After forming a (film thickness of 10 nm), a silicon dioxide film (film thickness of 100 nm) was formed, and the adhesion of the silicon dioxide film was evaluated.

Comparative Example 5 The hydrophilization treatment by corona discharge in Example 1 was not performed (the contact angle of pure water on the resin substrate surface was 90 degrees), and the primary coating was not performed. 0.4P, targeting glass
Under the argon atmosphere of a, a high frequency of 500 W was applied to the target. ) To form a silicon dioxide film (film thickness 100n)
m) was formed. When the adhesion of the obtained silicon dioxide film was evaluated, almost the entire surface of the portion where the cellophane tape was stuck was peeled off.

Comparative Example 6 A plasma treatment was performed on the polyethersulfone substrate manufactured by ICI (company) used in Example 1 in the same manner as in Example 9 so that the contact angle of water on the resin substrate surface became 20 degrees. I made it. Using the coating solution of Comparative Example 1, a primary coating film (thickness: 10 nm) was formed in the same manner as in Example 1;
A silicon dioxide film (film thickness: 100 nm) was formed in the same manner as described above, and the adhesion was evaluated in the same manner as in Example 1. As a result, almost the entire surface of the portion to which the cellophane tape was attached was peeled off.

Comparative Example 7 The maximum output was about 140 using the apparatus of Example 1 on the polyethersulfone substrate manufactured by ICI (company) used in Example 1.
A corona discharge treatment at a variable voltage of 00 volts and a frequency of about 15 kHz was performed at a rate of 5 mm per second so that the contact angle of water on the surface of the polysulfone substrate was 40 degrees. Then, both silanes were mixed at a ratio of B / A = 0.2, wherein the weight (B) in terms of tetraethoxysilane SiO _{2 was the} weight in terms of SiO _3/2 (A) of 3-methacryloxypropyltrimethoxysilane. A 1% ethyl alcohol solution was prepared, and an amount of water necessary for hydrolyzing the methoxy group was further added, followed by sufficient stirring to obtain a coating solution. The coating liquid was applied to the resin substrate subjected to the corona discharge treatment by a dipping method, and was naturally dried to form a primary coating having a thickness of 10 nm. Thereafter, a silicon dioxide film (100 nm thick) was formed on the resin substrate by the same method as in Example 1, and the adhesion was evaluated by the same method as in Example 1.
Almost all of the portion stuck with cellophane tape was peeled off.

Comparative Example 8 After the surface of the polysulfone resin substrate was hydrophilized (water droplet contact angle was 70 degrees) in the same manner as in Example 1 except that the corona discharge treatment speed was set to 100 mm / sec, 3 A primary coating (10 n thick) in the same manner as in Example 1 except that 0.4 wt% of vinyltriethoxysilane was used instead of methacryloxypropyltrimethoxysilane.
m), and a silicon dioxide film (film thickness 100 n)
m), but no uniform silicon dioxide coating was obtained.

Comparative Example 9 3-methacryloxypropyltrimethoxysilane was added to 0.1%
An ethanol solution containing 4% by weight and 0.4% by weight of 3-aminopropyltrimethoxysilane was prepared, and water required for hydrolyzing the hydrolyzable groups was added thereto. And After the surface of the polysulfone resin substrate was hydrophilized in the same manner as in Example 1 (water droplet contact angle was 40 degrees), a 10 nm-thick primary film was formed in the same manner as in Example 1 using the above coating solution. Formed. afterwards,
In the same manner as in Example 1, a silicon dioxide film (film thickness 100 n
m), but no uniform silicon dioxide coating was obtained.

Comparative Example 10 3-methacryloxypropyltrimethoxysilane was added to 0.1%
An ethanol solution containing 4% by weight and 0.04% by weight of 3-aminopropyltrimethoxysilane is prepared, and an amount of water necessary for hydrolyzing the hydrolyzable group is added,
The mixture was sufficiently stirred to obtain a coating solution. After the surface of the polysulfone resin substrate was hydrophilized in the same manner as in Example 1 (water droplet contact angle was 40 degrees), a 10 nm-thick primary film was formed in the same manner as in Example 1 using the above coating solution. Formed. Thereafter, a silicon dioxide film (film thickness 10) was formed in the same manner as in Example 1.
0 nm), but a uniform silicon dioxide film could not be obtained.

COMPARATIVE EXAMPLE 11 An ethanol solution containing 0.4% by weight of vinyltriethoxysilane was prepared, and an amount of water necessary for hydrolyzing the hydrolyzable group was added thereto. did.
After the surface of the polysulfone resin substrate was hydrophilized in the same manner as in Example 1 (water droplet contact angle was 40 degrees), a 10 nm-thick primary film was formed in the same manner as in Example 1 using the above coating solution. Formed. Thereafter, a silicon dioxide film (thickness: 100 nm) was formed in the same manner as in Example 1, and the adhesion of the film was evaluated in the same manner as in Example 1. The entire surface peeled off. The above Examples and Comparative Examples are summarized in Tables 1 to 3, respectively.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

[Table 3]

As is clear from the results shown in Tables 1 to 3, in the examples of the present invention, silicon dioxide having very good adhesion to the substrate surface and good surface coating property with respect to the polysulfone resin was used. A thin film has been formed. In particular, it has been found that good adhesion can be ensured by making the contact angle of water 65 ° or less in the hydrophilization treatment.

[0102] In general formula (1), looking at the compound of (2), methacryloxysilane, vinylsilane, but allylsilane resistance relatively higher than the _H 2 SiF _6, aminosilane whereas _H 2 SiF ₆ Not resistant. But,
Aminosilane has relatively high adhesiveness to polysulfone that has been hydrophilized, while methacryloxysilane and
Vinylsilane and allylsilane were found to have relatively low adhesion.

[0103]

According to the present invention, the polysulfone resin, particularly the polyethersulfone resin, has very good adhesion to the substrate surface, has excellent gas permeability prevention properties (water permeability prevention properties), and has excellent surface coating properties. Since a favorable silicon dioxide film can be formed, a resin substrate for liquid crystal display, a liquid crystal display element, and the like satisfying precise dimensional stability can be obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuhito Sakai 3-15-11 Doshomachi, Chuo-ku, Osaka-shi, Osaka Inside Nippon Sheet Glass Co., Ltd. (72) Inventor Hodaka Norimatsu 3 Doshomachi, Chuo-ku, Osaka-shi, Osaka No. 15-11, Nippon Sheet Glass Co., Ltd. F-term (reference) 2H090 JA06 JB03 JC07 JD11 JD12 4F006 AA40 AB67 AB76 BA05 CA05 DA04 EA03 4F073 AA01 AA31 BA32 BB02 CA01 CA21 CA45 CA62 EA01 EA11 EA63

Claims (8)

[Claims] A first coating comprising an organosilicon compound is applied to a polysulfone resin, and a solution containing hydrosilicic acid in which silicon dioxide is in a supersaturated state is brought into contact with a substrate to form a first coating on the first coating. A method for producing a resin substrate for a liquid crystal display, comprising forming a silicon dioxide film on a substrate. 2. The method according to claim 1, wherein a surface of the polysulfone resin is subjected to a hydrophilic treatment prior to the formation of the primary coating. 3. The above-mentioned primary coating is represented by the general formula (1) R ¹ _n Si (R ² ) _4-n (1) where R ¹ is an organic functional group having a methacryloxy group, and R ² is One or more hydrolyzable groups selected from an alkoxyl group, an acetoxyl group and chlorine, and n is a coating liquid containing a silicon compound having an organic functional group represented by an integer of 3 or less or a hydrolyzate thereof. The method for producing a resin substrate for a liquid crystal display according to claim 1, wherein the resin substrate is obtained by drying afterwards. 4. The above-mentioned primary coating is represented by the following general formula (2): R ³ _n Si (R ² ) _4-n (2) wherein R ³ is selected from a methacryloxy group, a vinyl group, an allyl group and an amino group. R ² is one or more hydrolyzable groups selected from an alkoxyl group, an acetoxyl group and chlorine, and n has an organic functional group represented by an integer of 3 or less. The liquid crystal display according to claim 1, wherein the liquid is obtained by applying a coating liquid containing a plurality of different silicon compounds or hydrolysates thereof among the silicon compounds or hydrolysates thereof, followed by drying. A method for manufacturing a resin substrate. 5. The method for producing a resin substrate for a liquid crystal display according to claim 1, wherein at least one of the plurality of silicon compounds contained in the coating liquid is a silicon compound having an amino group. 6. The method according to claim 1, wherein the proportion of the silicon compound having an amino group is 0.01% among the plurality of silicon compounds contained in the coating solution.
The method for producing a resin substrate for a liquid crystal display according to any one of claims 1, 2, 4 and 5, wherein the amount is from 70 to 70% by weight. 7. A resin substrate for a liquid crystal display obtained by the manufacturing method according to claim 1. 8. A liquid crystal display element comprising the liquid crystal display resin substrate according to claim 7.