JP3473840B2 - Window glass for vehicles with oxide film and method of manufacturing - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a window glass for a vehicle with an oxide film, which can be used for a front window, a rear window, a side window, etc. for a vehicle, and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, for the purpose of protecting the comfort of the vehicle such as heat ray shielding and ultraviolet ray shielding, designability, privacy protection, etc., for vehicles with a functional film in which the surface of the window glass of an automobile is coated with a functional film. Window glass is widely adopted.
In addition, recently, various products having hydrophilicity, antifogging property and antifouling property due to the photocatalytic effect of titanium oxide have been developed, and many patents relating to architectural or automatic window glass and the like have been filed.

For example, Japanese Patent No. 2756474 discloses a base material having a hydrophilic photocatalytic surface on the surface of which a photocatalytic coating containing a photocatalytic semiconductor material and silica is made hydrophilic by photoexcitation. Japanese Patent Laid-Open No. 9-22715
No. 9 discloses a front and rear window glass of a vehicle having a transparent, photocatalytic semiconductor material-containing layer bonded to the surface of a substrate.
Japanese Patent Application Laid-Open No. 10-60665 discloses a hydrophilic coating containing titania obtained by coating and baking a composite solution containing a metal oxide sol containing titania and colloidal silica in which the shape of the sol is a chain is disclosed in Japanese Patent Application Laid-Open No. 10-231146. In the publication, there is known an antifogging and antifouling glass article in which an alkali barrier film and a photocatalyst film are laminated on the surface of a glass substrate and irregularities are formed on the surface of the photocatalyst film.

[0004]

A photocatalyst film is formed on the entire outer glass surface of a vehicle rear window by a wet method, and then heated to form a glass in a desired shape at the same time as the photocatalyst film is baked. When bent and / or strengthened,
There is a problem that a desired glass bending curvature shape cannot be obtained.

[0005]

As a result of various investigations in view of the above-mentioned problems, the inventors of the present invention have found that when a photocatalyst film is formed on the entire surface up to the periphery of glass, the photocatalyst film is subjected to thermal processing such as firing or bending / strengthening. When the film contracts, the contraction force at that time is applied to the peripheral edge of the glass and a predetermined bending curvature shape and reflection distortion cannot be obtained, and if the oxide film is formed in the area excluding the outer peripheral portion of the predetermined width from the peripheral edge of the glass. It has been found that even if the oxide film is baked or heat-treated, a predetermined bending curvature shape and reflection distortion can be obtained.

That is, in the window glass for a vehicle with an oxide film of the present invention, an oxide film is formed in a region of the glass surface on the outside of the vehicle except the outer peripheral portion of a predetermined width, and the outer peripheral portion of the predetermined width is oxidized. It is characterized in that it is a non-influenced portion of the shrinkage force due to heating and firing of the material film.

Further, the vehicle window glass with an oxide film of the present invention is characterized in that the oxide film is a photocatalyst film containing titania crystals and has a hydrophilic property and / or an antifouling property.

Further, the window glass for a vehicle with an oxide film of the present invention is characterized by being bent and / or strengthened.

Further, the method for producing a window glass for a vehicle with an oxide film according to the present invention includes a method for producing a window glass for a vehicle with an oxide film having a desired glass curvature shape by the following steps. A feature of the present invention is to prevent defective curvature due to the contraction force of the film. (1) A step of applying an oxide film forming coating solution to form a film on a region of a vehicle window glass excluding an outer peripheral portion having a predetermined width from a peripheral edge of a vehicle outside glass surface, and (2) forming an oxide film. A step of forming an oxide film by heating and baking glass.

Further, the method for producing a window glass for a vehicle with an oxide film of the present invention is characterized in that the formed oxide film is heated and baked and the glass is bent at the same time.

Furthermore, in the method for producing a window glass for a vehicle with an oxide film according to the present invention, the temperature is lower than the temperature at which the oxide film is formed and then heated and baked before heating and baking.
It is characterized in that it is calcined at a temperature of 0 ° C to 620 ° C.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The window glass for a vehicle of the present invention usually has a bent shape and is convex outward. Further, in consideration of safety against glass breakage at the time of collision, when glass breaks, it is strengthened so that it becomes a small piece. The heat processing temperature for this bending and / or strengthening is suitably about 560 to 700 ° C,
Since it is in the same temperature range as the firing of the formed oxide film,
At the same time as baking the formed oxide film, bending and / or bending of the glass
Alternatively, it is preferable to perform heat processing for strengthening. In addition,
In some cases, after bending the oxide film, bending and / or
Alternatively, thermal processing for strengthening can be performed. In addition, before the film firing, bending, and strengthening as described above, the temperature is set to about 550 to 620 ° C., which is a temperature at which the glass does not soften and which is as high as possible and lower than the firing temperature. It is also possible to hold for 30 minutes and perform calcination.

In the window glass for a vehicle of the present invention, an oxide film is formed on a region of the glass surface on the outside of the vehicle excluding the outer peripheral portion of a predetermined width, and the outer peripheral portion of the predetermined width is heated and baked. It is characterized in that it is a non-influenced part of the contraction force. When the entire surface of the glass is covered with an oxide film formed on the glass surface outside the vehicle, heat shrinkage occurs during baking of the film, and glass having a predetermined bending curvature shape and reflection distortion cannot be obtained. The region of the outer peripheral portion where the oxide film is not formed has a width sufficient to obtain a predetermined bending curvature and reflection distortion depending on the type of film, the bending curvature of glass, and the like. The width is preferably 15 mm or more in the case of a back window, for example.

The vehicle window glass on which the oxide film of the present invention is formed can be manufactured, for example, by the following steps. (1) A step of applying an oxide film forming coating solution to form a film on a region of a vehicle window glass excluding an outer peripheral portion having a predetermined width from a peripheral edge of a vehicle outside glass surface, and (2) forming an oxide film. A step of forming an oxide film by heating and baking glass.

As the oxide film formed on the glass surface outside the vehicle, a metal oxide containing at least one kind of Si, Ti, Zr, Sn, Zn, Ta and the like can be used.
These oxide films are heat ray shielding films, depending on the purpose and application.
UV shielding film, hydrophilic antifogging film, antifouling film, electromagnetic wave shielding film,
Functions such as a non-reflection film, a radio wave transmission film, a conductive film, and a decoration film can be appropriately selected.

Among them, in the case of a photocatalyst film containing at least TiO ₂ crystals, it is photoexcited by ultraviolet rays and exerts functions such as hydrophilicity, antifogging property and antifouling property. There is a need. In addition to TiO ₂ , other oxides such as SiO ₂ , Al ₂ O ₃ , ZrO ₂ , SnO ₂ ,
CeO _{2 and the} like may be contained, and considering the durability used for the vehicle exterior glass surface for vehicles, SiO ₂ , Al ₂ O ₃ ,
A film composition containing at least one ZrO ₂ is preferable. The S
This is because iO ₂ has a function of improving the wear resistance of the oxide film, and ZrO ₂ has a function of improving chemical resistance such as alkali resistance and water resistance. Besides the alkali resistance is improved with the addition of ZrO _2, since the addition of ZrO ₂ improves the photocatalytic activity preferred.

Any source containing TiO ₂ crystals after firing may be used as the TiO ₂ source, and in particular, powdered TiO ₂ fine particles for photocatalyst or a chemical solution as commercially available may be used. Examples of the body-shaped photocatalyst TiO ₂ fine particles include ST-01, ST-21 (manufactured by Ishihara Techno), SSP-25, SSP-20 (manufactured by Sakai Chemical Industry),
PC-101 (Titanium Industry), Super Titania F
-6, Super Titania F-5 (manufactured by Showa Titanium), DN-22A (manufactured by Furukawa Kikai Metal) and the like can be used. Examples of the photocatalyst chemical solution include STS-01, STS-02 (manufactured by Ishihara Techno), and P.
It is also possible to use C-201 (manufactured by Titanium Industry Co., Ltd.) A-6, M-6 (manufactured by Taki Chemical Co., Ltd.) and the like, and ST-K which is a mixture of TiO ₂ fine particles for photocatalyst and silica raw material.
01, ST-K03 (manufactured by Ishihara Techno) and the like can also be used.

As the other oxide raw material, for example, in the case of a SiO ₂ raw material, any material may be used as long as it produces silicon oxide after firing, and examples thereof include tetramethoxysilane, tetraethoxysilane, and methyltrimethoxysilane. , Stabilized with an alkoxysilane such as methyltriethoxysilane, a hydrolyzate or polycondensate thereof, and a stabilizer such as acetylacetone, and a commercially available silica chemical solution such as Colcoat P (made by Colcoat), MS
H2 (manufactured by Mitsubishi Chemical), CSG-DI-0600 (manufactured by Chisso) or the like can be used, and other raw materials for oxides can also be metal alkoxides or their hydrolyzates, like TiO ₂ or SiO ₂ . Or a polycondensate and those stabilized with a stabilizer such as acetylacetone, and commercially available chemicals can be used according to the purpose.
When alkoxides are used, inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid are mainly added as the hydrolysis catalyst.

The coating solution further contains a solvent, which can dissolve alkoxides and metal salts, for example, alcohols such as methanol, isopropyl alcohol, ethanol, ethylene glycol oligomer, polyethylene glycol. , Propylene glycol oligomer, diols such as hexylene glycol, water, cellosolve, carbitol and the like can also be used. In addition, in the coating liquid,
For example, other raw materials such as a thickener may be contained.

The method for forming the oxide film is not particularly limited, but dip coating method, spin coating method, roll coating method, bar coating method, spray coating method, flexographic printing method, screen printing method, etc. The film can be formed by the general film forming method of. When forming a film by the printing method, it is not necessary to mask the outer peripheral portion of the glass peripheral edge, but when forming a film by a wet method other than that, mask the part not to be formed beforehand with a masking film or UV curable resin. There is a need to.

The film formed is finally 560 ° C. to 70 ° C.
Firing at a temperature of 0 ° C., Si, Ti, Zr, Sn, Zn,
A functional film made of at least one kind of metal oxide such as Ta is firmly adhered to the glass surface so as to give durability such as abrasion resistance and chemical durability necessary for practical use.

The thickness of the oxide film is 50 nm to 1000 nm
If so, for example, in the case of a photocatalyst film, the formed photocatalyst film has photocatalytic activity and high durability, but more preferably, by setting the film thickness to 50 nm to 500 nm,
It is more preferable because an oxide film having good translucency and higher durability can be obtained by one-time film formation.

As the glass, a commonly used soda lime silicate composition is generally used. Colored glass colored with clear or other glass composition such as blue, gray, bronze, green, etc., vapor-deposited on the glass surface inside the car Various processes such as attaching metal films, metal filaments, oxide films, resin films, etc. by coating such as spattering, printing, etc., processing the inside glass surface by etching, sand blasting, etc. and combining them Does not matter. The thickness of the glass is generally 2 to 5 mm for a vehicle, but is not limited to this. The vehicle-mounted window glass with an oxide film of the present invention is a front window glass, a rear window glass, a hydrophilic side glass for a side window glass, an antifogging property,
It is suitable because it can sufficiently exhibit functions such as antifouling property,
It can also be used for window glass of other parts. In addition, the oxide film-car window glass of the present invention may be a flat plate in some cases, and may not be strengthened in some cases.

When a dark colored film is formed on the outer peripheral portion of the glass surface on the inside of the vehicle to shield the terminal lead-out portion of the anti-fogging wire or antenna wire and the mounting portion for mounting the glass on the vehicle body, It is particularly preferable in view of appearance that the dark colored film is formed in a region of the outer peripheral surface of the vehicle outside glass surface where the oxide film is not formed and in a region of the outer peripheral portion of the vehicle inside glass surface facing the region. When the visible light reflectance and the color tone of the external appearance of the oxide film such as the photocatalyst film formed on the outside glass surface of the vehicle are different from those of the glass substrate, the outside area of the outside glass surface of the vehicle and the outside of the vehicle If the area of the dark colored film on the outer peripheral portion of the inner glass surface partially overlaps, when the dark colored film is viewed from the exterior of the vehicle, the color tone looks different from the original color tone and the appearance deteriorates. If both areas of the outer peripheral portion do not overlap and a gap is left, there may occur a case that is not preferable in terms of function or appearance. Further, an antenna wire and / or a conductive wire or the like may be formed in the central region of the glass surface inside the vehicle where the dark colored film is not formed.

The window glass for a vehicle with an oxide film of the present invention comprises:
By providing a photocatalytic function by using a photocatalytic film containing titania crystals as an oxide film, when the ultraviolet rays contained in sunlight or fluorescent lamps are irradiated, the organic substances attached to the surface of the film are decomposed by the photocatalytic effect and the film is formed. Has the effect of keeping the surface of the surface clean (called oxidative decomposition type reaction), and
The iO ₂ surface is also hydrophilized (called a superhydrophilic type reaction). This phenomenon is particularly preferable because it has the function of improving the visibility in rainy weather.

[0026]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. Regarding the obtained vehicle window glass,
The following evaluations were made [Evaluation method] A zebra pattern written in white lines on a reflective distortion black board is prepared, and the zebra pattern is reflected on the outside of the glass car. Evaluation,
Passed (○), semi-defective (△), and rejected (×) glass with the same distortion as the glass of the desired shape without the oxide film formed.
And

Curvature The glass was placed on an inspection table having a desired shape, and a gap (deviation in shape) between the periphery of the glass and the inspection table was measured.
As for the evaluation, if the deviation of the shape is within 2 mm, it passes (○) and 2 mm
Anything over the mark was rejected.

Example 1 Vehicle glass with a photocatalyst film made of an oxide was manufactured by the following steps.

Preparation of Coating Solution for Forming Photocatalyst Film ZrOCl ₂ (manufactured by Kishida Chemical Co., Ltd.) was used as the ZrO ₂ source of the coating solution.
CSG-DI-0600 (manufactured by Chisso), T for SiO ₂ source
to iO ₂ particle source and SiO ₂ source ST-K01 (TiO _2:
SiO ₂ = 8: 2 weight ratio, manufactured by Ishihara Techno), and ethanol (manufactured by Kishida Chemical Co.) and 1-methoxy-2- were used as a solvent.
Using propanol (manufactured by Kishida Chemical Co., Ltd.), the photocatalyst film has an oxide component ratio of 10ZrO ₂ · 40SiO ₂ · 50TiO ₂
(Wt%).

1000 mm × 18 which was thoroughly washed with water, detergent and ceria
A float glass plate (green color) having a size of 00 mm × 3.5 mm (thickness) was used as a raw glass plate. Then, a portion corresponding to the outer peripheral portion of the outer glass surface of the final glass after cutting described below (corresponding to outer peripheral portion 4 shown in FIGS. 1 and 2 described later, 40 mm width at the narrowest portion, and at the widest portion) 70 m
m width)) and the entire surface of the vehicle inner glass surface was masked with a masking tape, and the photocatalyst film was formed by the dip coating method using the coating chemical solution prepared above. The masking tape was removed immediately after the film formation.

Formation of vehicle window glass A glass sample with a photocatalyst film on the outside glass surface
Is calcined at a glass temperature of 600 ° C. for 5 minutes, and then predetermined
Cut glass into shape and seam the glass edge
It was Then, by the screen printing method, the glass surface inside the car
At the outer peripheral part (12 part shown in FIGS. 1 and 2 described later)
Black ceramic membrane with the desired design (black dark
Color film) was formed. The black ceramic film is made of Cr, Mn,
Lead borosilicate containing spinel pigment composed of Cu element
A frit-containing paste was deposited. Furthermore, silver paste
Heat ray of desired pattern by screen printing method using
The antenna wire is formed in the center of the glass surface inside the vehicle. Next
At 650 ° C, the photocatalyst film is baked and the glass is bent / strengthened.
Oxide film, black ceramic
The film, heat wire, and antenna wire are sintered and fixed to the glass surface,
Photocatalytic film with a thickness of 200 nm (10ZrO₂・ 40 SiO₂
・ 50 TiO ₂(Wt%)) coated back win
A window glass for a vehicle for dough was obtained.

The obtained window glass for a vehicle with an oxide film is
As shown in FIG. 1 (partial plan view of the vehicle window glass as viewed from the outside of the vehicle) and FIG. 2 (cross-sectional view of the vehicle window glass), the vehicle window glass 1 has a glass peripheral edge of an outside glass surface 2. Predetermined outer peripheral part 4 from 3 (4 from the glass periphery at the narrowest part
The photocatalyst film 5 is formed in the central region except the width of 0 mm and the width of 70 mm at the widest part, and the outer peripheral portion corresponding to the outer peripheral portion 4 from the glass peripheral edge 3 of the vehicle interior glass surface 11 has a dark black color. The colored film 12 is formed, and the heating wire 13 is printed in the central portion.

The obtained window glass for a vehicle with an oxide film was evaluated by the above-mentioned method. As a result, as shown in Table 1, the sample had desired reflection distortion and curvature. Further, the photocatalytic performance required for hydrophilicity and antifouling property was satisfied.

[0034]

[Table 1]

(Embodiment 2) As shown in FIG. 3 (cross-sectional view of a window glass for a vehicle), a photocatalyst film 5 formed on a glass surface 2 on the outer side of a vehicle is removed from a center of a glass peripheral edge 3 except an outer peripheral portion 4 having a width of 15 mm. The same procedure as in Example 1 was performed except that the region was set. As a result, as shown in Table 1, the sample had desired reflection distortion and curvature. Further, regarding the performance, the durability was so high that it could be used for a window glass for a vehicle (the film side is the outside of the vehicle).

(Example 3) The same procedure as in Example 1 was carried out except that the film forming region was the central region excluding the outer peripheral portion having a width of 10 mm from the peripheral edge of the glass having a predetermined shape to finally become the window glass. As a result, as shown in Table 1, the curvature was acceptable, but the reflection distortion was a little worse than in Examples 1 and 2.

(Comparative Example 1) The procedure of Example 1 was repeated except that the film-forming region was the entire outer surface of the vehicle exterior glass. As a result, as shown in Table 1, both reflection distortion and curvature were unacceptable.

[0038]

INDUSTRIAL APPLICABILITY The vehicle window glass with an oxide film of the present invention has an excellent appearance when a functional film such as a photocatalyst is formed on the outer surface of the vehicle without causing shape defects and reflection distortion due to film shrinkage. The effect is that a window glass having a desired shape can be obtained.

[Brief description of drawings]

FIG. 1 is a partial plan view of a vehicle window glass obtained in Example 1. FIG.

FIG. 2 is a cross-sectional view of a vehicle window glass obtained in Example 1.

FIG. 3 is a sectional view of a vehicle window glass obtained in Example 2.

[Explanation of symbols]

1 Vehicle window glass 2 car outside glass surface 3 glass edges 4 outer peripheral part 5 Photocatalytic film 11 Inside glass surface 12 Dark colored film 13 heat rays

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiro Nishida 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Glass Research Laboratory (56) Reference JP-A-11-140434 (JP, A) JP-A-10- 324545 (JP, A) JP-A-9-208244 (JP, A) Patent 2756474 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) B60J 1/00 B01J 35/02 C03B 23 / 023 C03C 17/23

Claims (6)

(57) [Claims] 1. An oxide film is formed in a region of a glass surface on the outside of a vehicle except a peripheral portion having a predetermined width, and the peripheral portion having a predetermined width is a portion which is not affected by shrinkage force due to heating and firing of the oxide film. A window glass for a vehicle having an oxide film, which is characterized in that 2. The window glass for a vehicle with an oxide film according to claim 1, wherein the oxide film is a photocatalyst film containing titania crystals and has a hydrophilic property and / or an antifouling property. 3. The window glass for a vehicle with an oxide film according to claim 1 or 2, wherein the window glass for a vehicle is bent and / or strengthened. 4. Oxidation which prevents curvature failure due to the shrinkage force of the film toward the peripheral edge of the glass when manufacturing a window glass for a vehicle with an oxide film having a desired glass curvature shape by the following steps. A method for manufacturing a window glass for a vehicle with a physical film. (1) A step of applying an oxide film forming coating solution to form a film on a region of a vehicle window glass excluding an outer peripheral portion having a predetermined width from a peripheral edge of a vehicle outside glass surface, and (2) forming an oxide film. A step of forming an oxide film by heating and baking glass. 5. The glass is bent at the same time when the formed oxide film is heated and baked.
A method for producing a vehicle window glass having the oxide film described above. 6. After the oxide film is formed, it is heated to a temperature of 300 ° C. to 62 ° C., which is lower than the temperature for heating and baking before heating and baking.
The method for producing a window glass for a vehicle with an oxide film according to claim 4 or 5, wherein the calcination is performed at a temperature of 0 ° C.