JPH09208266A - Method for coating surface of glass with organic polymer and glass coated with organic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain glass coated with an org. polymer with excellent adhesive strength independently of the kind of the polymer by forming a porous layer on the surface of glass, applying an org. polymer soln. to the porous layer and heat-treating this layer at a specified temp. SOLUTION: A porous layer is formed on at least one face of glass, an org. polymer soln. consisting of an org. polymer and a solvent capable of dissolving the polymer is applied to the porous layer and this layer is heat-treated at the m.p. or glass transition temp. of the org. polymer or above to coat the glass with the org. polymer. The porous layer is preferably formed by firing an org.-glass hybrid produced by a sol-gel method.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a glass having a porous layer coated with an organic polymer and a method for coating the organic polymer.

[0002]

2. Description of the Related Art In researching and developing a method for coating an organic polymer on the surface of glass, those skilled in the art will refer to the polymer coating method that has been conventionally performed on metals and the like. For example, various attempts have heretofore been made for polymer coating on the surface of a metal substrate, and in particular, a fluororesin coating is performed for the purpose of preventing metal corrosion. Specifically, a method has been adopted in which the surface of a metal base material is treated with enamel and then a fluororesin primer is applied and dried, and a fluororesin is applied and baked. Further, in order to improve adhesion and durability, one or a combination of glass, enamel glaze or ceramic glaze frit is used, and a mixture mixed with a foaming agent is applied to the surface of the base material, dried and baked to decompose the foaming agent. There is also an undercoating method for forming a porous undercoating layer having irregularities on the surface thereof (JP-A-58-70867).

[0003]

However, even if the glass surface is treated with this method and coated with a fluororesin, the adhesion is weak and the durability is not sufficient. On the other hand, regarding the polymer coating on the glass surface, for example, a polymer having a hydrogen bond such as polyamide or polyvinyl alcohol, or a polymer having a silanol group (SiOH group) and reacting with the Si-OH group on the glass surface is Even plate glass that does not have ordinary porosity can be strongly bonded to some extent. However, it was very difficult to bond other polymers (organic polymers) to the plate glass.

Therefore, the present invention solves the above-mentioned problems, and any organic polymer, particularly an organic polymer which cannot be coated on glass with a strong adhesiveness by the conventional method, is provided. It is also an object to provide a glass and organic polymer coating method coated with excellent adhesion.

[0005]

In order to solve the above problems, the glass according to the present invention has a porous layer and an organic polymer layer coated on the porous layer, and further, The organic polymer layer is a layer coated by applying a solution containing the organic polymer on the porous layer and then performing a heat treatment at a melting point or glass transition temperature of the organic polymer or higher. And

[0006] Preferably, the porous layer is a layer made of a porous material obtained by firing an organic / glass hybrid prepared by a sol-gel reaction.

The organic polymer coating method according to the present invention is a method of coating the surface of glass with an organic polymer, which comprises a step of providing a porous layer on at least one surface of the glass, the organic polymer and the organic polymer. A step of applying an organic polymer solution consisting of a solvent in which the system polymer is soluble to the porous layer, and the porous layer coated with the organic polymer at a melting point or glass transition temperature of the organic polymer or higher. A heat treatment step.

Preferably, the porous layer is obtained by firing an organic / glass hybrid produced by a sol-gel reaction.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a method of coating an organic polymer on the surface of a glass plate is provided with a porous layer on the surface of the glass plate, and after applying a polymer solution to the porous layer, A glass coated with an organic polymer is obtained by heat treatment at a melting point or glass transition temperature of the polymer or higher.

As a method for providing the porous layer on the surface of the glass plate, any known method can be used. In particular,
A method of treating the surface of a glass plate with a supersaturated aqueous solution of silica hydrofluoric acid (JP-A-57-166337), S
A method of coating and firing a solution of two kinds of precursor sols having different average molecular weights (thousands and hundreds of thousands) as an i oxide raw material solution and firing (JP-A-5-147976), a silicon dioxide film on the glass surface. A deposition (LPD) method of forming a porous layer by forming a film and a method using a glass-hybrid are known.

Here, a method of using the glass-hybrid will be described. In this method, an organic polymer and a silicic acid compound are dissolved in a solvent for a sol-gel reaction, a sol-gel reaction is performed with an acid catalyst to obtain a glass-hybrid, and a glass-hybrid obtained by this step is used. It is applied to the surface of the glass plate and is baked at a temperature at which SiO ₂ is not melted to form a porous layer. When the porous layer is formed by this method, it is easy to arbitrarily change the porosity and the thickness, so that the reflectance can be freely controlled. A typical method for producing a glass-hybrid by a sol-gel reaction is described in JP-A-6-509131. The number of pores in the porous layer formed on the surface of the glass plate is 1
0 to several 1000 nm, preferably 10 to 100 nm
nm. The larger the number of pores in this porous layer, the better the adhesion of the polymer.

The polymer solution applied to the porous layer is a polymer selected depending on the purpose of coating and dissolved in a solvent in which the polymer can be dissolved. A polar polymer such as polyamide which forms a hydrogen bond with a glass surface can be coated on a normal flat glass surface with good adhesion without using the coating method of the present invention. However, when coating a non-polar polymer or fluorine-based polymer that does not have hydrogen bonds or chemical bonds with the glass surface, use a solvent that is selectively determined from the polymer used to form a polymer solution, apply it, and heat-treat it. By doing so, coating can be performed with good adhesion. The windshield of cars, the glass of buildings, and even the polymers that have hydrogen bonds or chemical bonds with the glass surface will adhere even more strongly. Fluorine-based polymers are preferably used when transparency, stain resistance, and anti-fog properties such as glasses are required.When coloring glass or UV protection, polymethylmethacrylate or polystyrene is used. Agents or UV stabilizers can be mixed and used.

The polymer selected according to the purpose of coating is dissolved in a solvent in which the polymer can be dissolved and applied to glass having a porous layer. A typical example of polyamide is formic acid, which dissolves well when coating a non-polar polymer or a fluoropolymer.

The organic polymer solution comprising the organic polymer and a solvent in which the polymer can be dissolved is applied by a known method such as a dipping method, a spray method, a spin coating method or the like. The heat treatment temperature after applying the polymer solution is
It is determined according to the polymer used. In the case of a crystalline polymer, the heat treatment is performed at the melting point of the polymer or higher, and in the case of an amorphous polymer, the heat treatment is performed at the glass transition temperature or higher. The heat treatment may be performed by any known method, for example, using an oven or a vacuum oven.

For example, when a glass having a porous layer is coated with a fluorine-containing polymer represented by the following general formula (1) (Teflon SF manufactured by DuPont), this fluorine-containing polymer is preferably a fluorine-containing solvent, preferably 3M. A polymer solution dissolved in Fluorinert CF-75 manufactured by Co. is applied on the porous layer and then heat-treated at a temperature of 40 ° C. or higher.

[0016]

Embedded image

Further, another fluoropolymer represented by the following general formula (2) (Teflon AF1600 manufactured by DuPont) is used.
Or 2400) coated porous glass,
After coating a polymer solution prepared using the above solvent on glass having a porous layer, 160 ° C. or higher for Teflon AF1600 and 240 ° C. for Teflon AF2400.
It is manufactured by heat treatment at the above temperature.

[0018]

Embedded image

Further, the glass having a porous layer coated with polymethylmethacrylate or polystyrene is produced by applying a polymer solution prepared by using tetrahydrofuran as a solvent and then firing it at a temperature of 100 ° C. or higher.

Specific examples of the present invention and comparative examples will be described below.

[0021]

【Example】

Example 1 A glass coated with an organic polymer according to the present invention was prepared as follows.

That is, glass (AR glass, manufactured by Nippon Sheet Glass Abi Co., Ltd.) on the surface of which a porous layer was formed by the LPD method was used, and the organic polymer shown in Table 1 below and A polymer solution consisting of a solvent in which the polymer can be dissolved is applied. In this example, subsequently, a heat treatment is performed at a temperature above the melting point or glass transition temperature of the polymer. The coating of the polymer solution is performed by Lauda film lift (Fi
lm Lift) by the dipping method. Therefore, the rate of pulling up the porous glass from the polymer solution was set to three, and the influence of each pulling rate was also investigated.

For comparison, a slide glass manufactured by Matsunami Co., Ltd. was used as a normal plate glass, and the same operation was performed to prepare a polymer-coated glass for comparison.

Example 2 A glass porous layer coated with an organic polymer according to the present invention was prepared by the sol-gel method as follows.

2-hydroxyethyl methacrylate 3
7.3 mol%, butyl acrylate 36.3 mol%,
Consists of 20 mol% styrene, 2 mol% methyl methacrylate, 2 mol% isobutyl methacrylate, 2.4 mol% methacrylate (manufactured by DuPont Automotive), number average molecular weight of about 11,000, glass transition point 3
A polymer at 0 ° C. was used, and an acrylic polymer solution was obtained as a solution having a composition of 65% by weight of polymer, 30% by weight of xylene, and 5% by weight of methyl ethyl ketone.

20 g of the acrylic polymer solution, 30 g of tetraethoxy silicate, 20 g of 2-butoxyethanol and 10 g of 2-propanol were mixed and uniformly dissolved. Add 8 g of HCl (36%) aqueous solution and 6 parts of pure water.
The mixture with g was added slowly, and the mixture was stirred at room temperature for about 4 hours and a half. The liquid exothermed during this reaction.

A glass substrate which had been sequentially washed with a neutral detergent, water, alcohol, acetone, etc., and was then dipped in this solution was pulled up at a pulling speed of 30 mm / min or 100 mm / min and left overnight at room temperature. The polymer solution deposited on top was agar-like. This is 12
After vacuuming at 0 ° C. for 1 hour, it was baked at 600 ° C. for 20 minutes to form a porous layer.

[0028]

[Table 1]

In Table 1, the Teflon SF copolymer is composed of Teflon SF (manufactured by DuPont), 43 mol% HFP, and 57 mol TFE. Fluorinert CF-75 is a fluorine-based solvent manufactured by 3M. Further, PS666 and PMMA560F manufactured by Asahi Kasei Corporation were used as polystyrene and polymethylmethacrylate, respectively. Also,
Viton AHV is (HFP / TFE / VDF terpolymer).

A tape peeling test and a tape peeling test were carried out on the coated glass thus obtained in Examples 1 and 2 and after making a grid pattern.

In the tape peeling test, Nichiban cellophane tape, 3M scotch tape 810 and 3M scotch tape 898 were adhered to glass and peeled repeatedly 10 times to examine the peeled state of the coated film.

Similarly, in the cross-cut peeling test, the cut surface of the coating surface of the coated glass is cut with a cutter knife to reach the glass surface.
100 squares of m × 1 mm are formed. After making such cuts, the tape surface is forcibly peeled off 10 times for each tape using the above-mentioned adhesive tape.

Regarding the results of the tape peeling test and the cross-cut tape peeling test, "○" was given when peeling was not observed, and "△" was observed when peeling was found in a part of a 1 mm square rectangle. ], And more than 1m 1m
Tables 2 to 4 below show the case where the m-sided square itself is almost completely peeled off as "x".

With respect to the transparency of the coating glass, good one was marked with "◯", and poor one was marked with "x".

The slide is a slide glass (manufactured by Matsunami Co., Ltd.), the AR is glass having a porous layer formed on the surface by the LPD method (manufactured by Nippon Sheet Glass Abi Co., Ltd.), and the hybrid is a porous by the sol-gel method. By layered glass is meant.

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

As is clear from Tables 2 to 4, the glass coated with the polymer according to the method of the present invention showed excellent peel resistance without impairing transparency as compared with the conventional glass.

[0040]

As described above, glass having a porous layer is coated with a polymer solution containing an organic polymer and a solvent capable of dissolving the polymer, and then the melting point of the polymer or By performing the heat treatment at the glass transition temperature or higher, it is possible to obtain the effect that the adhesiveness and the peeling resistance of the coated organic polymer film are remarkably higher than those of the conventional ones.

Claims (4)

[Claims] 1. A solution comprising a porous layer and an organic polymer layer coated on the porous layer, wherein the organic polymer layer is a solution containing the organic polymer on the porous layer. After being applied, the glass is a layer coated by performing heat treatment at the melting point or glass transition temperature of the organic polymer or higher. 2. The glass according to claim 1, wherein the porous layer is a layer made of a porous body obtained by firing an organic / glass hybrid prepared by a sol-gel reaction. 3. A method for coating glass with an organic polymer, comprising the step of providing a porous layer on at least one surface of the glass, and the organic polymer comprising an organic polymer and a solvent in which the organic polymer is soluble. A glass surface comprising a step of applying a solution to the porous layer, and a step of heat-treating the porous layer coated with the organic polymer at a melting point or glass transition temperature of the organic polymer or higher. Method for coating organic polymer on glass. 4. The method for coating an organic polymer on a glass surface according to claim 3, wherein the porous layer is obtained by firing an organic / glass hybrid produced by a sol-gel reaction.