JPH0848542A - Reinforced and/or bent glass plate for interrupting ultravoilet rays - Google Patents

Abstract

PURPOSE:To produce a bent glass, reinforced glass or reinforced bent glass having a UV rays interrupting film strong and excellent in weather resistance. CONSTITUTION:The UV rays interrupting reinforced and/or bended glass plate has the UV rays interrupting layer formed by applying a soln. containing ultraviolet-absorbing metal oxide particulates and poly (perhydrosilazane) in a ratio of 20:80 to 90:10 on a reinforced and/or bent glass plate and heating the coated film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet ray blocking glass plate, and more particularly to an ultraviolet ray blocking glass for vehicles manufactured by a reinforced bending process.

[0002]

2. Description of the Related Art As a vehicle glass provided with an ultraviolet absorbing layer, Japanese Patent Laid-Open No. 3-223111 discloses an ultraviolet absorbing glass in which zinc oxide is used as an ultraviolet absorbing film and a protective film such as silicon oxide or zirconium oxide is coated on the outside thereof. Has been done. Also, JP-A-4-192327
Is provided with an ultraviolet absorbing layer containing zinc oxide on the substrate,
There is disclosed a surface-treated glass having an ultraviolet absorbing ability, which is obtained by undercoating or overcoating a metal oxide film.

Further, Japanese Patent Laid-Open No. 5-339033 discloses an ultraviolet ray blocking glass obtained by dispersing a zinc oxide fine powder in an organopolysiloxane solution, applying the obtained solution to a glass plate, and firing at 580 to 700 ° C. In JP-A-5-345638, a coating solution containing a cerium salt complexed with a chelate ligand, a silicon compound, and a titanium compound as main components is coated on a glass substrate and then heated to a temperature of 300 ° C. or higher. The ultraviolet absorbing glass by doing so is disclosed.

Further, Japanese Patent Laid-Open No. 5-163174 discloses cerium oxide.
There is disclosed an ultraviolet absorbing glass in which a scratch-resistant protective film such as polysilazane is provided on the ultraviolet blocking layer made of titanium oxide / silicon oxide.

These are characterized in that they are formed by a method of coating an ultraviolet absorbing layer and a protective layer before the bending strengthening step (herein referred to as a Coat Then Bend method).

On the other hand, JP-A-6-145387 discloses an ultraviolet-absorbing transparent body having a silicone-based coating film on a synthetic resin-based primer coating formed by dissolving and adding a fluorescent whitening agent and an organic UV-absorbing agent. It is disclosed. In addition, JP 4-
160037 discloses a method for blocking ultraviolet rays of an automobile glass by applying a resin solution containing an organic ultraviolet absorber.

[0007] These are characterized in that they are formed into a film by a method of coating an ultraviolet absorbing layer and a protective layer on the glass after undergoing a bending strengthening process (herein referred to as "bend then coat"). There is.

[0008]

There are forming methods such as press bending and self-weight bending in the step of strengthening and / or bending a glass plate for a vehicle, etc., but all of them are heated above the softening point of the glass, that is, above 600 ° C. It is generally done. In the strengthening process, air-cooled strengthening is generally used, and a method in which glass heated above the softening point is rapidly cooled by an air blow is adopted. J.AMER
According to ICAN CERAMIC SOCIETY 73 [1] 3-14 (1990), since the solgel film undergoes extremely large volume shrinkage during each process of gelling, drying and sintering, the film after firing has very large compressive stress. It is said to have.

In the above-mentioned coat-send method, a so-called solgel film is applied before the strengthening and bending step, dried at a temperature of 200 ° C. or lower, and then fired in the bending and strengthening step to densify the film. When the glass exceeds the softening point, it is pulled toward the film due to the internally generated stress of the zolgel film and warps. The degree of this warpage largely depends on the thickness of the film, and depending on the thickness of the film, glass cracking or strain occurs in the bending strengthening process. Further, in the air-cooling strengthening process, when the difference in expansion coefficient between the film and the glass is large, wrinkles and cracks are generated in the film.

JP-A-5-339033 and JP-A-5-34
In 5638, increasing the film thickness increases the UV blocking effect, but at the same time, it cracks glass during the strengthening bending process,
Since distortion, wrinkles, cracks and the like are likely to occur, the ultraviolet blocking ability is naturally limited, and the degree of freedom in the film structure design is impaired.

Further, in the above-mentioned JP-A-3-223111, in order to secure the acid resistance of the zinc oxide film, it is devised to provide a protective layer containing silicon oxide as a main component in a thickness of 1 μm or more. As a result, there is a problem that the glass is cracked, warped, and distorted during bending strengthening.

On the other hand, since the bend-den-coat method is applied to a glass that has already been reinforced by bending, there is no above-mentioned problem caused by the coat-end-bend method, but the curing temperature of the ultraviolet blocking film increases the stress of the glass. Below the temperature at which it is not relaxed
Since the temperature must be set below 300 ° C,
The methods described in 6-145387 and Japanese Patent Application Laid-Open No. 4-160037 have a drawback that sufficient film strength cannot be obtained. Also, because it uses an organic UV absorber,
There has been a problem that yellowing and bleeding occur due to long-term use.

It is an object of the present invention to solve these problems and provide a bent glass, a reinforced glass and a reinforced bent glass having a strong and weather resistant ultraviolet ray blocking film by a bend-dense coat method. .

[0014]

The present invention is directed to strengthening and / or bending a solution containing ultraviolet absorbing metal oxide fine particles and poly (perhydrosilazane) in a weight ratio of 20:80 to 90:10. It is an ultraviolet blocking strengthened and / or bent glass plate having an ultraviolet blocking layer formed by coating the surface of a processed glass plate and heating the coating film.

In the present invention, the solution applied to the surface of the glass plate which has been strengthened and / or bent contains ultraviolet absorbing metal oxide fine particles and poly (perhydrosilazane). Ultraviolet-absorbing metal oxide fine particles are zinc oxide, titanium oxide, cerium oxide, and titanium oxide / cerium oxide composite oxide having a particle size of about 5-10.
Fine particles of 0 nm are used, and these are generally commercially available.

Further, poly (perhydrosilazane) is a kind of polysilazane, for example, J. AMERICAN CERAMIC SOC.
IETY, 73 [1] 170-172 (1990) or JP-A-5-163174
Can be synthesized by the method disclosed in. The poly (perhydrosilazane) has a number average molecular weight of 500.
Those of 10,000 to 10,000 are preferably used. In particular, Japanese Patent Laid-Open No. 5-238827 discloses an example of synthesizing tetramethoxysilane-added poly (perhydrosilazane) capable of obtaining a dense and highly hard film even at a low temperature treatment of about 150 ° C. These poly (perhydrosilazanes) are, for example, polysilazane PHPS manufactured by Tonen
-1 It is already on the market as a low temperature type.

The ultraviolet absorbing metal oxide fine particles are usually used by dispersing them in a solvent. The solvent is an aromatic hydrocarbon such as xylene, toluene or benzene, in which poly (perhydrosilazane) is easily dissolved, or ethyl ether. , Ethers such as tetrahistrofuran,
Halogenated hydrocarbons such as methylene chloride and carbon tetrachloride, or alkyl carbetyl acetate are preferable. These solvents may be used alone or in combination of two or more. It is necessary to remove the water content of the solvent beforehand. As the disperser, a sand mill or a paint shaker is suitable, and it is preferable to use Zylconvease. As a dispersant, a long-chain alkylphenyl surfactant such as sodium dedecylbenzene sulfonate, a hydrophilic polymer such as ammonium methacrylate, a polymer electrolyte, etc. may be added. The ultraviolet absorbing metal oxide fine particles may be directly dispersed in poly (perhydrosilazane) without using a solvent.

The UV-absorbing metal oxide fine particles after dispersion are mixed with a poly (perhydrosilazane) solution, stirred well, and then applied. It is also possible to add the fine particles directly to the poly (perhydrosilazane) solution and apply it to the disperser. Gelation of (perhydrosilazane) may occur.

In this solution, ultraviolet absorbing metal oxide fine particles and poly (perhydrosilazane) in a weight ratio of 2 are used.
Ratio of 0:80 to 90:10, more preferably 3
It is contained at 0:70 to 85:15. If the amount of UV-absorbing metal oxide fine particles is too small, the UV blocking performance tends to decrease, and conversely, if it is too large, the amount of poly (perhydrosilazane) decreases and the adhesion and durability of the UV blocking layer decrease. Easier to do. Further, the amount of the solvent is adjusted so that the solid component in the solution is usually 2 to 50% by weight.

After the substrate glass is strengthened and / or bent, it is polished and washed in advance with an abrasive such as cerium oxide (trade name Celico), sufficiently washed with water until there is no residual abrasive, and rinsed with pure water. It is desirable to keep it. It must be dried thoroughly so that water remains on the glass surface.

The coating of the above-mentioned solution and the coating of the poly (perhydrosilazane) for the protective layer described later can be carried out by using a coating apparatus such as a roll coater, a rubber coater, a bar coater, a die coater, a spin coater or a curtain coater. Alternatively, a spraying method, a pull-up method, a flow coating method, or the like may be used. Further, a printing method such as curved surface printing, flexographic printing, screen printing may be used.

After applying the above solution, 200 to 300 ° C.
After heating for 0.5 hours to 2 hours, the coating film is changed into an ultraviolet blocking layer made of dense silica in which ultraviolet absorbing metal oxide fine particles are dispersed and contained. UV blocking layer is 200-3000
It preferably has a thickness of nm. The above heating temperature is 30
If it exceeds 0 ° C, the thermal strain of the air-cooled glass may be lost, so it must be avoided.

In order to enhance durability, it is preferable to further coat a protective film solution containing poly (perhydrosilazane) on the UV blocking layer and heat it to provide a dense silica protective layer. In this case, after applying the solution for the ultraviolet blocking layer, it is air dried and then dried at 100 to 250 ° C. for 5 minutes to 1 hour.
By heating at 00 ° C. for 0.5 hours to 2 hours, the ultraviolet blocking layer and the protective layer are simultaneously formed. This protective layer preferably has a thickness of 500 to 5000 nm.

The above-mentioned solution for the protective film is used by dissolving poly (perhydrosilazane) in a solvent, and the same solvent as the above-mentioned solvent for dispersing the ultraviolet absorbing metal oxide fine particles can be used. The solid component (calculated as silica) in the protective film solution is usually adjusted to have a solvent amount of 2 to 50% by weight.

The application of the solution for the ultraviolet blocking layer and the solution for the protective film is preferably performed in a clean room, and further, is performed in a room where the relative humidity is controlled to 50% or less, preferably 20% or less. preferable.

[0026]

【Example】

Example 1 Poly (perhydrosilazane) (Polisilazane PHPS-1 low temperature type manufactured by Tonen (xylene solution, SiO2 solid content 6%)) was mixed with ZnO fine particles (particle size: about 50 nm) so that the total solid content was 70% by weight. The dispersed solution was placed in a polyethylene washing bottle as it was or after being diluted with xylene, and spray-flow coating was applied to one side of a 300 mm square, 3.5 mm thick soda lime type blue colored glass plate which had been subjected to the air-cooling strengthening treatment.

Heating was carried out by keeping in a high temperature electric dryer at 250 ° C. for 1.5 hours. The obtained ultraviolet blocking film had a structure in which ZnO fine particles were dispersed in a silica matrix, and the weight ratio of silica to ZnO in the film was 30:70, which was the same as the component ratio in the raw material solution. The UV transmittance and haze ratio at 350 nm and 370 nm are shown in Table 1 below. (Represented by T350, T370, and Hz, respectively) The film thickness was measured on the central portion of the coated glass by Alpha Step manufactured by Tenker. Further, the ultraviolet transmittance was measured by a UV-visible spectrophotometer Model 330 manufactured by Hitachi, and the haze ratio was measured by a direct-reading type haze computer manufactured by Suga Test Instruments.

[0028]

[Table 1] Table-1 Film Thickness and Optical Properties of Poly (perhydrosilazane) Containing Zinc Oxide Fine Particles ============================ == ZnO-containing polysilicane film thickness T350 T370 Hz (% of total solids) (nm) (%) (%) (%) ----------------------------------- −−−−−−− 20 (stock solution) 1055 0.7 6.9 0.1 15 795 2.1 12.3 0.1 10 370 10.8 20.4 0.1 ========================== ====

From the above results, it can be seen that in any of the examples, the ultraviolet rays are blocked by about 80% or more and the haze ratio is low.
In particular, it has been found that a very excellent UV blocking effect can be obtained by controlling the film thickness to about 1 micron using a 20 wt% coating solution.

Example 2 A solution in which ZnO fine particles were mixed and dispersed in poly (perhydrosilazane) (Polisilazane PHPS-1 low temperature type (xylene solution, SiO2 solid content 6%) manufactured by Tonen) so that the total solid content was 70% by weight. 300 ml as it is or after diluting with xylene, put it in a polyethylene washing bottle, and
A 3.5 mm thick soda lime type blue glass, which had been subjected to the air-cooling treatment at the corners, was spray-flow coated.

An ultraviolet absorbing layer was formed by drying in an electric dryer at 110 ° C. for 10 minutes. After that, poly (perhydrosilazane) (polyurethane low temperature type manufactured by Tonen Co., Ltd. (xylene solution, SiO2 solid content 20%)) as it is or diluted with xylene to an appropriate concentration was applied onto the ultraviolet absorbing layer by a similar method.
Heating was carried out by keeping in a high temperature dryer at 250 ° C for 1.5 hours. First, the protective layer film thickness was measured in the same manner as in Example 1. The results are shown in Table-2.

[0032]

[Table 2]

Next, after coating poly (perhydrosilazane) containing fine zinc oxide particles, a glass having a poly (perhydrosilazane) protective layer coated on the film was subjected to film thickness measurement, ultraviolet transmittance and haze ratio in Example 1. It measured similarly to. The results are shown in Table-3.

[0034]

[Table 3] Table-3 Thickness and optical characteristics of ultraviolet absorbing film =================================== ZnO-containing polysilazane Polysilica for protective layer Total film thickness T350 T370 Hz (Total solids wt%) (Total solids wt%) (nm) (%) (%) (%) --------------- −−−−−−−−−−−−−−−−−−−−−−− 10 20 3950 10.5 39.1 0.1 20 10 2275 0.9 10.2 0.6 15 10 2015 3.2 18.9 0.5 ========= ==========================

Even if the poly (perhydrosilazane) for the protective layer is applied and heat-treated after coating and drying the zinc oxide fine particle-containing poly (perhydrosilazane), it blocks about 60% or more of the ultraviolet rays and loses the ultraviolet blocking effect. There wasn't. Further, the appearance of the obtained coating film was also good with a haze ratio of 0.6% or less, no glass cracking or warping occurred, and no wrinkles or cracks were observed in the film.

Example 3 The glass with an ultraviolet blocking film produced in Examples 1 and 2 was subjected to the following test to evaluate durability. Table of results
-4. Acid resistance test The ultraviolet transmittance was measured before and after immersion in 0.2N sulfuric acid for 1 hour. Taber abrasion test Using the method described in JIS R3212, the change in haze value before and after 1000 abrasions was measured. Boil resistance test The ultraviolet transmittance was measured after immersion in boiling water at 100 ° C for 1 hour.

[0037]

[Table 4] Table-4 Results of durability test of ultraviolet blocking film ==================================== Before ZnO protection test Acid resistance, boiling resistance, taper, liquid with layer test after 1000 tests ----------------------------------- (wt%) (wt% ) T350 T370 Hz T350 T370 Hz T350 T370 Hz Hz (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) −−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−− 20 None 0.7 6.9 0.1 87.0 88.1 0.1 ---- --8.4 (*) 15 None 2.1 12.3 0.1- ---------- 4.2 10 20 10.5 39.1 0.1 10.5 39.1 0.1 ---- --1.7 20 10 0.9 10.2 0.6 0.9 11.4 0.2 1.1 12.5 0.4 1.6 15 10 3.2 18.9 0.5 3.2 19.8 0.3 2.9 20.7 0.7 1.4 =================================== (*) A part of the film was peeled off.

An ultraviolet blocking film consisting only of poly (perhydrosilazane) containing fine particles of zinc oxide is slightly inferior in acid resistance and tape abrasion resistance.
It was found that the ultraviolet blocking film provided with the protective film has improved acid resistance and abrasion resistance.

Example 4 A solution obtained by mixing and dispersing poly (perhydrosilazane) (Polisilazane PHPS-1 low temperature type manufactured by Tonen Co., Ltd. (xylene solution, SiO2 solid content 20%)) in fine particles of ZnO to a total solid content of 70% by weight. Was placed in a polyethylene washing bottle as it was or after being diluted with xylene, and was spray-coated on the inside surface (that is, the concave surface) of the automobile front door glass after reinforced bending (by the self-weight bending strengthening method). After drying in a large electric dryer at 110 ° C. for 10 minutes, poly (perhydrosilazane) (Polysilane low temperature type manufactured by Tonen Co., Ltd. (xylene solution, SiO 2 solid content 20%)) was applied to the upper layer by the same method. Drying was performed by keeping in a large-sized high temperature electric dryer at 250 ° C for 1.5 hours.

The appearance of the obtained coating film was good, no cracking, warping or distortion of glass was observed, and no wrinkles or cracks were found in the film.

When the glass for a door was destroyed by giving a strong impact, the glass was finely crushed and the property as a reinforced glass was maintained. The optical characteristics were measured using this fragment. The results are shown in Table-5. In the transmission characteristics, YA represents the visible light transmittance, and x and y represent the color difference of the transmitted light with the substrate glass. The reflection characteristic is performed on the film surface, RA is the visible light reflectance, and x and y represent the color difference between the reflected light and the substrate.

[0042]

[Table 5] Table-5 Optical Characteristics of UV Blocking Front Dust ====================== ZnO-containing liquid Protective layer liquid Solid content Film thickness Solid content Film thickness (wt%) (nm) (wt%) (nm) −−−−−−−−−−−−−−−−−−−−− 20 985 10 1330 =========== =========== =================================== Transmission characteristics Reflection characteristics (film Surface) YA T350 T370 xy RA xy (%) (%) (%) (%) (%) −−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−− 80.0 0.8 11.7 0.292 0.311 6.60 0.292 0.311 0.2 =================================== =

From Table 5, it can be seen that the glass for UV blocking front door has a high UV blocking performance, is colorless in both transmitted light and reflected light, and has low visible light reflectance.

Example 5 Poly (perhydrosilazane) (polyethylene low temperature type manufactured by Tonen)
PHPS-1 (xylene solution, SiO2 solid content 2%) with titanium oxide fine particles (particle size about 30-60 nm) and cerium oxide fine particles (particle size about 8)
A solution in which (.about.30 nm) was mixed and dispersed was directly or after diluted with xylene, put into a polyethylene washing bottle, and spray-coated on a 300 mm square soda lime type blue glass 3.5 mm thick.

Here, the molar ratio of titanium oxide and cerium oxide is
Mix so that the solid content of poly (perhydrosilazane) (that is, silicon oxide), titanium oxide, and cerium oxide will be 1: 2: 2 in molar ratio (about 12:32:69 in weight ratio). Added to become. Heating was carried out by keeping in a high temperature electric dryer at 250 ° C for 1.5 hours.

The thickness of the obtained ultraviolet blocking film, the ultraviolet transmittance at 350 nm and 370 nm (represented by T350 and T370) and the haze ratio are shown in Table 6 below. The film thickness, the ultraviolet transmittance and the haze ratio were measured by the same methods as in Example 1.

[0047]

[Table 6] Table-6 Film thickness and optical characteristics of titanium oxide / cerium oxide fine particle-containing polysilazane ============================== ==== Titanium oxide / cerium oxide-containing polysilazane film thickness T350 T370 Hz (total solids wt%) (nm) (%) (%) (%) −−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−− 19 (stock solution) 1218 1.1 15.1 0.4 15 655 2.3 22.3 0.4 10 305 10.8 31.8 0.3 =============== ===================

From the above results, the ultraviolet blocking film containing titanium oxide / cerium oxide fine particles showed a sufficient ultraviolet blocking performance although the ultraviolet transmittance was slightly inferior to the zinc oxide containing product shown in Example 1.

Further, when the durability was evaluated by the test method described in Example 3, it was found that good acid resistance and tape abrasion resistance were exhibited, and that it could be sufficiently used without the protective layer.

Example 6 The poly (perhydrosilazane) containing fine particles of titanium oxide and cerium oxide shown in Example 5 was put into a polyethylene washing bottle and subjected to a reinforced bending process (by the self-weight bending reinforced method) for automobile front door glass. Was spray-painted on the inside of the car.

Drying was carried out by keeping in a large high temperature electric dryer at 250 ° C. for 1.5 hours. The obtained ultraviolet-blocking glass had a slight yellow coloring, and although the reflection was somewhat high, no cracking, warping, distortion or the like was observed, and no wrinkles or cracks were observed in the film. The color of the glass was slightly yellowish.

Example 7 In order to improve the coloring and the high reflectance in Example 6, the surface of the inside of the vehicle front door glass after the reinforced bending process (by the self-weight bending reinforced method) was previously prepared in Example 1. The zinc oxide fine particle-containing poly (perhydrosilazane) shown below was applied by a flow coating method, dried at 110 ° C. for 10 minutes, and then the titanium oxide / cerium oxide containing poly (perhydrosilazane) shown in Example 6 was applied.
Was also applied by the flow coating method and dried at 250 ° C. for 1.5 hours. The film thickness was 700 nm in the lower layer and 2100 nm in the upper layer. When the obtained ultraviolet blocking front glass was visually observed, both the degree of coloring and the reflectance were lower than those of the glass prepared in Example 6.

Example 8 Poly (perhydrosilazane) (Polisilazane PHPS-1 made by Tonen Co., Ltd. low temperature type (xylene solution, SiO2 solid content 12%)) was mixed with titanium oxide / cerium oxide composite fine particles (particle size: about 50-100 nm, oxidation). A solution in which a composition ratio of titanium / cerium oxide (weight ratio: 50/50) was mixed at 40% by weight ratio of total solid content was dispersed as it was or after diluted with xylene, and then put into a polyethylene washing bottle to obtain a 300 mm square soda lime system. A blue glass 3.5 mm thick was spray-coated on one side.

Heating was carried out by keeping in a high temperature electric dryer at 250 ° C. for 1.5 hours. The thickness of the obtained ultraviolet blocking film and 35
UV transmittance at 0 nm and 370 nm (T350, respectively)
T370) and haze ratio are shown in Table 7 below. The film thickness, the ultraviolet transmittance and the haze ratio were measured by the same methods as in Example 1.

[0055]

[Table 7] Table-7 Film thickness and optical characteristics of titanium oxide / cerium oxide fine particle-containing polysilazane ============================== = Titanium oxide / cerium oxide composite fine particle-containing polysilicane film thickness T350 T370 Hz --------------------------------------- (total solid content wt %) (Nm) (%) (%) (%) −−−−−−−−−−−−−−−−−−−−−−−−−−−−− 20 (stock solution) 1058 2.1 18.6 1.1 15 550 2.8 32.7 0.8 10 305 8.8 41.8 0.7 ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝

From the above results, the ultraviolet blocking film containing titanium oxide / cerium oxide composite fine particles showed an ultraviolet blocking function although the ultraviolet transmittance was slightly inferior to the zinc oxide containing product shown in Example 1.

Further, when the durability was evaluated by the test method described in Example 3, it was found that good acid resistance and tape abrasion resistance were exhibited, and that it could be used without a protective layer.

Comparative Example 1 To 150 g of cerium nitrate hexahydrate, 104 g of acetylacetone was added and reacted at 90 ° C. for 1 hour while stirring. This is the first liquid. 50g of ethyl silicate (Ethyl silicate 40 made by Colcoat) is added to isopropanol
44 g and 0.2 g hydrochloric acid aqueous solution 6 g were added, and the mixture was reacted at room temperature for 12 hours. This is the second liquid. 18 g of acetylacetone was added to 50 g of tetrafluoropropyl titanate and reacted at room temperature for 12 hours. This is the third liquid. The first liquid, the second liquid, and the third liquid have a Si / Ti / Ce molar ratio of
Mix so that the ratio is 1: 2: 2, and use isopropanol to adjust the total solid content ratio.
It was diluted to 8.3%.

A 300 mm square soda lime type blue glass 3.5 mm thick was coated on one side with a muskin sheet to masquerade, and this solution was applied by a diff lifting method. 30 at 110 ℃ in an electric dryer
After minute drying, the glass was suspended in an electric furnace having an ambient temperature of 760 ° C. and heated, and after 120 seconds, taken out and allowed to cool in the atmosphere, the glass was warped with the film side being a concave surface. The film thickness at this time was about 200 nm.

Comparative Example 2 Instead of allowing the glass taken out of the furnace to cool in the atmosphere, when the glass plate temperature reached around 650 ° C., the curvature of 10
The same operation as in Comparative Example 1 was carried out except that a press molding was performed so that the film surface became a concave surface by pressing a 00 mm two-dimensional bending mold, and the glass could be molded in a shape close to that of the mold. As compared with the case where a glass without a film was similarly molded, distortion was recognized in the peripheral portion.

Comparative Example 3 100 parts by weight of methyltriethoxysilane, 100 parts by weight of isopropyl alcohol, 30 parts by weight of pure water and 0.1 part by weight of concentrated hydrochloric acid were placed in a 500 ml round bottom flask equipped with a stirrer and a reflux condenser, respectively, and an oil bath was added. At 150
The reaction was carried out for 2 hours while maintaining at ℃ to obtain a viscous transparent liquid. Next, this liquid was distilled under a reduced pressure of 5 to 20 mmHg to obtain 37 parts by weight of a white solid. 30 parts by weight of this white solid, 70 parts by weight of zinc oxide fine particles of O.1 μm or less, ethyl acetate
100 parts by weight, 100 parts by weight of butyl carbitol acetate and 50 parts by weight of toluene were mixed and dispersed in a sand grinder for 3 hours to obtain a white liquid.

This solution was applied to a 300 mm square soda lime type blue glass 3.5 mm thick by a spin coating method. 110 in electric dryer
After drying at ℃ for 30 minutes, this glass was hung in an electric furnace with an atmospheric temperature of 760 ℃ and heated, taken out after 120 seconds and allowed to cool in the atmosphere, the glass was greatly warped with the film side being concave. . The film thickness at this time was about 400 nm.

Comparative Example 4 Instead of allowing the glass taken out of the furnace to cool in the atmosphere, when the glass plate temperature reached around 650 ° C., the curvature of 10
The same operation as in Comparative Example 1 was carried out except that a press molding was performed so that the film surface became a concave surface or a convex surface by pressing a 00 mm two-dimensional bending die, and in both cases, the glass cracked and the molding was could not.

Comparative Example 5 Tonen's polysilazane PHPS-1 low temperature type (SiO2 solid content 20%) for the protective layer used in Example 2 was put in a polyethylene washing bottle, and a 300 mm square soda lime type blue glass 3.5 mm thick one side It was sprayed on and flow coated. After drying in an electric dryer at 110 ° C for 30 minutes, suspending and heating in an electric furnace with an atmospheric temperature of 760 ° C, 120 seconds later, the air blown from the blower was blown out from the nozzle to quench and strengthen it. Has a concave surface on the side of the film and is largely warped, and wrinkles and cracks are observed on the surface of the film.

[0065]

EFFECTS OF THE INVENTION According to the present invention, a vehicle having an ultraviolet ray blocking film, which is free from warp or distortion in glass, has no wrinkles or cracks, has high hardness and is excellent in weather resistance, by low temperature heat treatment at 250 ° C. or less. A bent glass, a reinforced glass, and a reinforced bent glass suitable for a window glass for use can be obtained.

Claims (3)

[Claims] 1. A surface of a glass plate, which has been strengthened and / or bent, with a solution containing ultraviolet absorbing metal oxide fine particles and poly (perhydrosilazane) in a weight ratio of 20:80 to 90:10. An ultraviolet-shielding strengthened and / or bent glass plate having an ultraviolet-shielding layer formed by coating and heating the coating film. 2. The coating film is dried before the heating,
The ultraviolet ray shielding enhancement and / or bending according to claim 1, further comprising an ultraviolet ray shielding layer and a protective layer formed by further coating a solution for a protective layer containing poly (perhydrosilazane) and heating both coating layers. Glass plate. 3. The ultraviolet absorbing metal oxide fine particles are at least one selected from the group consisting of zinc oxide fine particles, titanium oxide fine particles, cerium oxide fine particles, and titanium oxide / cerium oxide composite fine particles. A UV-shield strengthened and / or bent glass plate as described.