JPH09227168A - Ultraviolet screening glass and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject glass applicable to various areas as a pane for building or automotive use by providing the surface of a glass base plate with neutral color-toned two-layer film so as to bear excellent functionality such as ultraviolet screening performance and radio wave transmitting performance, abrasion resistance and chemical resistance on the glass plate. SOLUTION: This ultraviolet screening glass is obtained by providing the surface of a glass base plate with a 1st layer ZnO-SiO2 -based thin film 1.5-1.8 in refractive index (n1 ) and <=1.5μm in thickness (t1 ) followed by laminating the 1st layer with a silicone-based hard coating film 1.4-1.5 in refractive index (n2 ) and >=1μm in thickness (t2 ).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly has excellent ultraviolet ray shielding performance, has little transparency in coloring and interference colors, has good transparency, is excellent in durability and radio wave transmission, and has various functions. TECHNICAL FIELD The present invention relates to an ultraviolet-shielding glass composed of a two-layer film capable of having appropriate properties and a method for producing the same.

The present invention provides a useful ultraviolet ray shielding glass which can be used not only as architectural glass but also as automobile glass, at least as a single plate, and a method for producing the same.

[0003]

2. Description of the Related Art In recent years, from the viewpoint of preventing sunburn of human bodies and interior materials in architectural glass and vehicle glass, conventional glass does not impair the color tone and transparency, and has a radio wave transmission property similar to that of a metal film. There is a need for a glass that has ultraviolet shielding performance without being damaged.

On the other hand, a coil using a metal oxide
The development of single-plate coated glass with a coating agent has been vigorously carried out, and the following are known, especially those using ZnO, which has an excellent ultraviolet absorption capacity.

For example, Japanese Patent Application Laid-Open No. 1-245201 discloses an ultraviolet cut filter, and discloses that a thin film made of zinc oxide is provided on at least one surface of a transparent substrate. Among them, for example, a benzene solution is prepared by dissolving 5 wt% of zinc octylate in terms of zinc oxide concentration on the uneven surface of a transparent substrate having a surface roughness of 1 to 5 μm formed by sandblasting or acid etching and dipping. It is described that the zinc oxide thin film was obtained by pulling at a constant rate after drying by the method, drying at 100 ° C., and baking at 500 ° C.

Further, for example, in Japanese Patent Laid-Open No. 2-75683,
An ultraviolet and infrared absorber and a method for treating the same are described, and an ultraviolet and infrared absorber for glass in which 0.01 μm to 1 μm white or light-colored metal oxide fine particles are dispersed in a polymer material-containing solution is disclosed. ing. Among them, it is described that the metal oxide fine particles are one or two simple substances of ZnO ₂ and TiO ₂ or a compound containing these, for example, an ultraviolet absorber made of Zn ₂ SiO ₄ .

Further, for example, Japanese Patent Application Laid-Open No. 4-182327 discloses that
A surface-treated glass and a method for producing the same are described.The surface-treated glass is provided with a ZnO-containing ultraviolet absorbing film having a thickness of 0.5 μm or more containing ZnO.
There is disclosed a method for producing a surface-treated glass in which a liquid containing a raw material which can be applied to a glass substrate is applied to the glass substrate, which is baked and, at the same time, the glass substrate is strengthened and / or bent.

[0008] Among them, glass whose substrate contains Na ⁺ ,
Forming a metal oxide film as an undercoat or overcoat film of an ultraviolet absorbing film, automotive window glass using the surface-treated glass, and ZnO as a composition of the coating film. It is disclosed that a film obtained by holding the above ultrafine particles with a silicone-based inorganic binder is used as a thick film composition.

Further, for example, in Japanese Patent Laid-Open No. 5-339033,
A method for producing an ultraviolet blocking glass, a window glass for automobiles, and a window glass for buildings are described. Zinc oxide fine powder having a particle size of 0.1 μm or less is added to an organopolysiloxane solution to form SiO ₂
/ZnO=0.25 to 0.67 (weight ratio)
The liquid obtained by dispersing the zinc oxide fine powder was applied to the plate glass so that the dry film thickness would be 0.2 to 1.5 μm, and
Thereafter, it is disclosed that the plate glass is fired at 580 to 700 ° C.

Further, for example, in Japanese Patent Laid-Open No. 5-345642,
UV shielding glass is described, an ultraviolet shielding film made of zinc oxide is formed on both sides or one side of the glass, and an organic solvent solution of polycarbosilane or polymetallocarbosilane is applied onto the ultraviolet shielding film, and It is disclosed that a protective film formed by firing is formed.

Further, for example, Japanese Patent Application Laid-Open No. 5-147978, which the applicant of the present invention has already proposed, discloses an ultraviolet absorbing glass having an ultraviolet absorbing film on glass and an oxide film as an outer coating. Contains at least zinc oxide, and the outer coating consists of at least one oxide of silicon, zirconium or titanium.

Further, for example, in Japanese Patent Application Laid-Open No. 5-163174, which has already been proposed by the present applicant, in an ultraviolet blocking glass for a vehicle in which glass is strengthened and / or bent,
Disclosed is a UV-shielding glass for vehicles, in which at least one ultraviolet absorbing film is formed on glass, and a layer containing silicon is formed on the outside, and the layer containing silicon has at least CH ₃ -Si bond. It has been described that the compound and / or the compound having a Si—N bond is applied and formed.

[0013]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, the ultraviolet cut filter described in Japanese Patent Application Laid-Open No. 1-245201 and the ultraviolet and infrared absorbents described in Japanese Patent Application Laid-Open No. 2-75683 and a method for treating the same are Although it has excellent UV blocking performance, it has poor chemical resistance to acids and alkalis and has a problem of durability when used outdoors. Especially, it is used for automobile window glass because it also has poor wear resistance. It doesn't reach the point. .

Further, for example, the surface-treated glass and the method for producing the same described in Japanese Patent Laid-Open No. 4-182327 satisfy ultraviolet absorption ability, abrasion resistance, acid resistance and alkali resistance, as is apparent from the examples. The thickness of the ZnO thin film is 1.5
If the undercoat and overcoat are required in the case of μm, or the overcoat is required when the film thickness of the ZnO thin film is 2.5 μm, the ultrafine particles of ZnO are assumed. Was used as a thick film composition, and SiO ₂ / ZrO ₂ with a close refractive index was simply overcoated with a thin film of about 0.1 μm in thickness. Even if the total film thickness is increased, the change in curvature and the generation of fine cracks cannot be avoided in the thermal bending strengthening process in the actual mass production of window glass for automobiles. And the development of interference color tone and wear resistance are substantially left.

Further, for example, the method for producing an ultraviolet blocking glass, the window glass for automobiles and the window glass for construction described in Japanese Patent Application Laid-Open No. 5-339033 are conventional ZnO as window glass for automobiles.
Although it is an improved ultraviolet blocking film than only a thin film, in the case of a single-layer film of the ultraviolet blocking film, it is practically necessary to have a rather thick film in the specified range. In order to withstand use in a more severe environment, for example, an overcoat that improves ultraviolet absorption ability, abrasion resistance, and chemical resistance while making the film thinner to suppress the generation of fine cracks. Etc. are required.

Further, for example, in the ultraviolet shielding glass disclosed in Japanese Patent Laid-Open No. 5-345642, only a protective film is formed on a conventional ZnO film having a film thickness of 0.5 to 5.0 μm, and it is true that the conventional protective film is used. It has better water resistance, acid resistance, and weather resistance than the ZnO thin film alone, and has improved durability.
As long as a membrane is used, it is hard to say that it can withstand longer-term use in a more severe environment.

Further, for example, in the ultraviolet absorbing glass described in Japanese Patent Application Laid-Open No. 5-147978, which the applicant of the present invention has already proposed, a protective film of silicon, zirconium or titanium is provided to improve the surface characteristics mechanically and chemically. However, similar to the one described in JP-A-4-182327 described above, the problem of film thickness, interference color, and the problem of matching with the heat bending strengthening process are insufficient, and as a window glass for automobiles, It is hard to say that it can withstand long-term use in harsh environments.

Furthermore, for example, in the ultraviolet blocking glass for vehicles described in Japanese Patent Application Laid-Open No. 5-163174 already proposed by the applicant of the present invention, although the protective film can be made stronger by using polysilazane, the cost is reduced. However, it is not always cheap, and it is hard to say that the recent automotive window glass needs have been fully cleared in mass production, making it suitable for longer-term use in more severe environments. Improvements have been awaited if it is possible to provide a sufficiently durable product at a low cost.

[0019]

SUMMARY OF THE INVENTION The present invention has been made in view of such a problem that a conventional ZnO-based coating glass has, and has a specific component having a specified refractive index and a specified film thickness. By providing an ultraviolet-shielding glass comprising at least two layers of an ultraviolet-absorbing film made of and a protective film made of a specific component having a specific refractive index and a specific film thickness, and a method for producing the same, it is possible to block ultraviolet light. It is possible to impart functional characteristics such as performance and radio wave transmission performance, and in addition, control the color tone of coloring, ensure transparency and prevent reflection and glare in a well-balanced manner, and obtain excellent quality,
It can be fired in various heat treatment processes, is cheap and easy, and can be freely adapted to the size and shape of glass. It exhibits durability such as excellent abrasion resistance and chemical resistance, and has a new film color tone.
A useful UV-shielding glass that can be applied to not only architectural window materials but also automotive window materials and that is suitable for recent needs, such as a toral color tone that can utilize the color tone of the glass substrate as it is, and its It provides a manufacturing method.

That is, according to the present invention, the glass substrate surface is
As the first layer, the refractive index n ₁ is 1.5 to 1.8 and the film thickness t ₁ is
A ZnO-SiO ₂ thin film having a thickness of 1.5 μm or less is formed, and the second layer has a refractive index n ₂ of 1.4 to 1.5 and a film thickness on the first layer.
An ultraviolet-shielding glass comprising a silicon-based hard coating film having a t ₂ of 1 μm or more, which is laminated by coating.

The ultraviolet shielding glass according to claim 1, wherein the ZnO-SiO ₂ thin film is formed from a solution containing zinc oxide fine particle silica binder as a main component.

As the silicon-based hard coating film, R ¹ _n Si (OR ² ) ₃ , R ³ Si (OR ⁴ ) ₃ and Si (OR ⁵ ) are used.
_An epoxy group-containing organosiloxane prepolymer obtained by hydrolyzing a partial condensation product of an alkoxysilane compound represented by ₄ [R ¹ : epoxy-containing alkyl group, R ² , R ³ , R ⁴ , R ⁵ : alkyl group] The ultraviolet-shielding glass described above, which is formed by forming a film from a solution containing-as a main component.

Further, the silicon-based hard coating film is formed from a solution containing a benzophenone-based ultraviolet absorber in a silicone-based hard coating film solution. The ultraviolet shielding glass described above.

On the surface of the glass substrate, a ZnO-SiO ₂ thin film solution was first applied as a first layer, and the temperature was kept at room temperature to 300 ° C for 0.
After drying for 5 to 60 minutes, baking at 400 to 700 ° C for 0.1 to 30 minutes gives a refractive index n ₁ of 1.5 to 1.8 and a film thickness t ₁ of 1.5 μm.
A ZnO-SiO ₂ thin film is formed as follows, and then the first
The second layer is coated with a silicone-based hard coating film solution, dried at room temperature to 100 ° C for 0.5 to 30 minutes, and then heat cured at 150 to 300 ° C for 0.5 to 60 minutes. do it,
A process for producing an ultraviolet-shielding glass, which comprises coating and laminating a silicon-based hard coating film having a refractive index n ₂ of 1.4 to 1.5 and a film thickness t ₂ of 1 μm or more.

Furthermore, the above-mentioned method for producing an ultraviolet-shielding glass, wherein the ZnO-SiO ₂ thin film solution is a solution containing zinc oxide fine particle silica binder as a main component.
Furthermore, the silicone-based hard coating film solution is R ¹ _n Si (OR ² ) ₃ , R ³ Si (OR ⁴ ) ₃ , Si (OR ⁵ ) ₄ [R ¹ : epoxy-containing alkyl Group, R ² , R ³ , R ⁴ , R ⁵ : alkyl group]
The method for producing an ultraviolet-shielding glass described above, wherein the alkoxysilane compound represented by the formula (1) is a solution containing an epoxy group-containing organosiloxane prepolymer as a main component obtained by hydrolyzing a partial condensate.

Furthermore, the silicon-based hardware
The method for producing an ultraviolet-shielding glass as described above, wherein the coating film solution is a solution containing a benzophenone-based ultraviolet absorber in a silicone-based hard coating film solution.

Further, as a method for applying the first layer solution, a spin coat method or a dip coat method is used.
The coating method, the reverse coating method, or the flexographic printing method, and the method for applying the second layer solution is a spin coating method, a dip coating method, or a spray coating method. A method for producing the above-mentioned ultraviolet shielding glass, which is characterized by:

Furthermore, ZnO-Si as the first layer is
A method for producing the above-mentioned ultraviolet-shielding glass is characterized in that the O ₂ -based coating film is fired at the same time in the steps of the heat bending treatment and / or the heat strengthening treatment of the glass substrate.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Here, as described above, a ZnO-SiO ₂ system having a refractive index n ₁ of 1.5 to 1.8 and a film thickness t ₁ of 1.5 μm or less as the first layer on the surface of a glass substrate. A thin film is formed, and the refractive index n ₂ is 1.4 to 1.2 as the second layer on the first layer.
5 and the thickness of the silicon-based harness with a film thickness t ₂ of 1.0 μm or more.
The following is carried out in order to carry out the ultraviolet shielding glass formed by coating and laminating the coating film.

Examples of the glass substrate include ordinary plate glass made of soda lime silicate glass, so-called float plate glass, which is generally used for automobile and architectural glass, and various colored glasses such as clear, green and bronze, and various types. It goes without saying that it can be used as functional glass, tempered glass or similar glass, laminated glass, multi-layer glass, and various flat glass products such as flat plates and bent plates. The plate thickness is, for example, about 1.0 m.
It is about m or more and about 12 mm or less, and about 2.
The glass is preferably about 0 mm or more and about 10 mm or less, more preferably about 1.5 mm or more and about 6.0 mm or less for automobiles, and more preferably about 2.0 mm or more and about 4.0 mm or less.

First, the ZnO-SiO ₂ system thin film of the first layer has no chromatic color of reflection as a thin film, a reflection interference color is hard to develop, and a neutral color tone is obtained even when combined with the second layer film. The film should be as thick as possible so that excellent UV absorption performance and improved film strength and chemical resistance can be expected, but the deterioration of adhesion due to firing, heat bending or / and heat strengthening, cracking, etc. are taken into consideration. The film thickness t ₁ to 1.5 μ
m or less, and also considering the adhesion with the second layer film
Since the ratio of the ZnO component to the SiO ₂ component may be changed, the refractive index n ₁ is set to the range of 1.5 to 1.8. For example, in order to make the refractive index n ₁ of the ZnO—SiO ₂ thin film after the heat bending strengthening treatment 1.62, the ZnO component should be appropriately adjusted to about 70 wt% and the SiO ₂ component to about 30 wt%. The film thickness t ₁ is preferably in the range of about 0.3 to 1.0 μm.

As a solution that can form a ZnO-SiO ₂ thin film,
For stability, for example, silica binder containing zinc oxide fine particles
And a solution similar to this solution, specifically, those manufactured by Sumitomo Osaka Cement Co., Ltd. and the like. Further, the ZnO component and the SiO ₂ component are solutions selected from various inorganic and / or organic substances and appropriately combined.

Next, regarding the second silicone-based hard coat film, even when combined with the first-layer ZnO-SiO ₂ thin film, it has a neutral color tone and excellent abrasion resistance. The film thickness t ₂ is 1.0 so that the first layer can be protected by chemical resistance.
It was set to about μm or more. Preferably, if the film is made too thick, cracks may occur during heat curing, and from an economic perspective, the film thickness t ₂ is about 1.5 to 3.0 μm, and the refractive index n ₂ does not include a special additive. As far as possible, the value is around 1.45, which is close to that of silica.

Further, as a silicone-based hard coat film solution, it has excellent coatability and adhesion to the lower layer ZnO-SiO ₂ -based thin film, and has excellent wear resistance and resistance to heating at a relatively low temperature. as having sufficiently chemical resistance, adhesion and low-temperature curability and film toughening the essential ^{_{R 1 n Si (oR 2)}} 3, R 3 Si (oR 4) 3, Si (oR 5) 4 [R ¹ : Epoxy-containing alkyl group, R ² , R ³ , R ⁴ , R ⁵ : alkyl group]
It is preferable to use a solution whose main component is an epoxy group-containing organosiloxane prepolymer obtained by subjecting an alkoxysilane compound represented by to a hydrolytic partial condensate, in order to further improve wear resistance and durability. It is also possible to add colloidal silica or the like. Silicon-based harbor of the composition
Although the docoating agent can be self-adjusted by a simple reaction, for example, Tosgard 510 [manufactured by Toshiba Silicon Co., Ltd.], Si Co
It is also possible to use G.T. In addition,
It goes without saying that it should not contain a strong acid or a strong alkali component that attacks the lower layer (first layer).

If a benzophenone-based UV absorber which is soluble in these liquids is added, the UV absorbing ability can be improved more easily. The more the ultraviolet absorber is added, the better. However, since the abrasion resistance of the second layer film is deteriorated, it is preferable that the ultraviolet absorber be contained in about 10% or less of the second layer film.

As a film forming method, the first layer of ZnO-Si is used.
The O ₂ -based thin film solution is not particularly limited, but from the viewpoint of productivity, for example, a spin coating method or a dip coating method, a reversal coating method, a flexo printing method, and A roll coating method, a nozzle coating method, a spray coating method, a screen printing method or the like can be appropriately adopted.

Specifically, for example, as the spin coat method for applying the solution, a solution having a solid content concentration of about 5 to 10% and a viscosity of about 1 to 5 cP is used, and is rotated at about 100 rpm or less, for example. On the other hand, about 50 to 150 ml / m ² of the solution is supplied from the nozzle to the central surface of the glass substrate, and the solution is spun off by rotating at about 200 rpm or less to form a film.

For example, as a dipping method for applying the solution, one surface of a glass substrate is masked, and the glass substrate with a mask is applied to the solution having a solid content concentration of about 10 to 20% and a viscosity of about 1 to 10 cP. After the immersion, the glass substrate is pulled up at a pulling rate of about 2 to 20 mm / sec to form a film.

Further, for example, a river for applying the solution
As the scoot method, when the solid content concentration is about 5 to 10%, the viscosity is
While circulating a solution of about 10 to 30 cP, a glass substrate is passed through a reversely rotating transfer roller at a conveying speed of about 3 to 5 m / min to form a film having a constant film thickness.

Further, for example, as a flexographic printing method for applying the above solution, a solution having a solid content concentration of about 20 to 40 wt% and a viscosity of about 20 to 200 cP is used, and a gravure roll is formed by a doctor roll and an anix roll. A glass substrate is conveyed at a rate of about 10 to 50 m / min by a gravure roll while being supplied to the film, and the solution is applied to form a film.

Further, the diluting solvent used in the above solution is a solvent containing a mixed solvent of isobutyl acetate and normal butanol as a main component in the spin coat method and the dipping method, and is used in the reverse coat method and the flexographic printing. In the method, a solvent containing hexylene glycol as a main component,
Or polyethylene glycol (average molecular weight 200),
Polypropylene glycol (average molecular weight 400) and the like have excellent film-forming properties and productivity.

Further, as the drying treatment in the above-mentioned coating, the drying temperature is from room temperature to 300 ° C. and the drying time is 0.
The drying temperature is preferably about 5 to 60 minutes, more preferably about 100 to 300 ° C and the drying time is about 1 to 50 minutes. It is preferable to carry out the treatment for about 20 minutes.

Further, the temperature for firing the laminated thin film is
The temperature may be about 400 to 700 ° C. for about 0.1 to about 30 minutes, and it may be performed simultaneously with the heat strengthening and / or heat bending of the glass. The heat strengthening or / and heat bending of the glass may be performed at the same time. More preferably, the temperature is about 500 to 700 ° C. and the time is about 0.5 to 10 minutes.

Further, the first baking treatment at the time of forming the film is carried out at a temperature of about 400 to 550 ° C. for about 5 to 60 minutes, more preferably the first baking treatment is carried out at a temperature of about 500 ° C. for about 10 to 20 minutes. Needless to say, a two-step firing method may be used, in which the heating is performed, and then the heating is performed at about 550 ° C. or higher for about 1 minute or longer.

Next, the second layer of silicon-based hardware
The coating method of the coating film solution is not particularly limited as in the case of the first layer, but from the viewpoint of productivity, for example, a spin coat method, a dip coat method or a spray coat method is used. , Further, a nozzle coat method, a roll coat method,
The flexographic printing method, the screen printing method and the like can be appropriately adopted. Among them, when a curved surface molded article is targeted, the dip coating method, the nozzle coating method, the spin coating method, the spray coating method, etc. G method is useful.

Specifically, for example, as a dip coating method for applying the solution, one surface of a glass substrate is masked, and the glass substrate with a mask has a solid content concentration of about 10 to 30% and a viscosity of about 1 to 10 cP. After immersion in the solution which is
The glass substrate is pulled up to form a film at a pulling rate of about 2 to 20 mm / sec.

Further, for example, the spin coating method for applying the above solution has a viscosity of 1 at a solid content concentration of about 10 to 20%.
Using a solution of about ~ 10 cP, while rotating at about 100 rpm or less, supply the solution of about 100 ~ 200 ml / m ² from the nozzle to the center surface of the glass substrate, and rotate at about 400 rpm or less to remove the excess solution. The film is formed by being shaken off.

Further, for example, as a spray-coating method for applying the above-mentioned solution, a solution having a solid content of about 5 to 20% and a viscosity of about 1 to 5 cP is used, and a nozzle diameter is 1.0 to
With an air spray gun of about 1.5 mmφ, the air pressure is 0.05 to 0.
About 15MPa (megapascal), flow rate about 40 ~ 120l / min, air ratio about 1,000 ~ 10,000, operating (moving) speed
The film is formed by deciding a pattern at about 30 to 60 cm / sec.

Further, the diluent solvent used for the solution may be selected from alcohols and cellosolves which are originally contained in the solution in consideration of the evaporation rate and viscosity of the solution.

Further, as the environment during the coating, it is preferable to use a clean room having a class of about 10,000 or more, a temperature of about 25 ± 5 ° C. and a relative humidity of about 40 to 60%. .

After coating in such an environment, about 5-30
Tack-free by drying for about 1 minute, then use a dryer such as hot air or far-infrared rays at 150-250 ° C for 10-60
Curing for about a minute is effective to prevent the occurrence of clouding (haze value) and cracks.

As described above, the ultraviolet shielding glass of the present invention and the method for producing the same include an ultraviolet shielding film which is a ZnO—SiO ₂ thin film having a specified refractive index and film thickness, and a specified refractive index and film on the film. By coating and laminating a protective film consisting of a thick silicon-based hard coating film, a neutral color tone can be obtained in which the effect of the laminated film itself on the color tone of the glass substrate can be reduced, and the ZnO is remarkably excellent. It is possible to make use of the ultraviolet (UV) absorption performance, and also to have excellent durability such as abrasion resistance and chemical resistance.
Since the O—SiO ₂ thin film can be subjected to heat strengthening and / or film bending and finishing at the same time as the heat bending treatment, the process can be simplified and the yield can be improved.

Further, as compared with the conventional bulk glass such as green glass having an ultraviolet absorbing ability, it is possible to have not only a marked ultraviolet ray blocking effect which is friendly to the environment and people but also a high visible ray transmittance. Yes, in addition AM
Because it can eliminate the influence of reception obstacles in the broadcasting of radio waves, FM radio waves, TV radio waves, etc., and because it has the same radio wave transmission performance as ordinary float glass, it is for TVs, radios, mobile phones, etc. for vehicles. It is possible to secure the comfortable environment inside and outside the vehicle by making the original glass antenna performance to be exhibited without reducing the reception performance of the glass antenna or reducing the radio interference such as ghost phenomenon. Therefore, it can be applied not only as a window material for construction but also as an automobile window material, for example, a front window, a rear window, a side window, a sunroof, etc., which is a useful ultraviolet shielding glass and its most suitable for recent needs. It provides a manufacturing method.

[0054]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment. [Preparation of Silicone Hard Coating Film Solution] The composition shown in Table 1 was applied to a 1000 ml round bottom flask equipped with a stirrer.
3-glycitoxypropyltrimethoxysilane (GPTMO
S), methyltriethoxysilane (MTEOS) and tetraethoxysilane (TEOS) are added, 0.5g of phthalic anhydride is added as a hydrolysis catalyst, and the mixture is heated to about 40 ° C in a hot water bath to dissolve it. IPA-ST, an organo-colloidal silica solution [Nissan Chemical Co., Ltd., SiO ₂ content approx. 30%] 16
Add 0 g, and then add 110 g of water at about 40 ° C for about 2
GPC [Tosoh Corporation, ULC802
A] with a number average molecular weight of about 1,000 and a solid content of about 30 wt%
A degree of composition was obtained.

50 P / W of a diluting solvent, isopropyl alcohol, was added to 100 P / W of the composition to obtain a composition having a solid content of about 20 wt%. Further, if necessary, the composition contains about 1 wt% of 2,2 ', 4,4' tetrahydroxybenzophenone (THBP) which is an ultraviolet absorber, and about 0.3 wt of dicyandiamide and sodium acetate, which are curing catalysts (CAT), respectively. % Added.

Example 1 Silica binder containing zinc oxide fine particles on a 3.5 mm thick clear glass substrate [ZnO / SiO ₂ = 70/30 weight ratio; ZnO average particle size of about 2 to 4 nm: Sumitomo Osaka Cement Co., Ltd.] Manufactured by diluting a mixed solvent of an ester compound such as isobutyl acetate and a high-boiling alcohol compound such as butanol as a diluent solvent so that the solid content concentration becomes about 10% by weight.
The coating solution for the ultraviolet absorbing film is 8 cP, and the glass substrate is coated with the ultraviolet absorbing film at 50 to 150 ml / m ² while rotating while appropriately adjusting the glass substrate at 30 to 60 rpm by the spin coat method. The solution is supplied to the central portion of the glass substrate to apply it, and further, the coating solution is shaken off and fixed by appropriately adjusting and rotating at 80 to 200 rpm to smooth and fix the coating film, and then at about 200 ° C. After being dried for 30 minutes and then baked in an electric furnace at about 620 ° C. for about 5 minutes, it was tempered by air cooling to prepare a tempered glass with a first layer film.

When the refractive index of the first layer film was measured by automatic ellipsometry (manufactured by Mizojiri Optical Co., Ltd.), the refractive index was about 1.
When the film thickness was measured with a stylus type film thickness measuring device (DekTak3030; manufactured by Sloan) at 67, it was a ZnO-SiO ₂ based thin film having a film thickness of about 800 nm.

Subsequently, the tempered glass substrate was adjusted at a rate of about 30 to 60 rpm by a spin coat method using the solution for the silicone type hard coating film prepared as described above at the ratio shown in Table 1. While rotating, about 100 to 200 ml / m ² of the solution was supplied to the center surface of the glass substrate (first layer film) from a nozzle, and further rotated at about 300 rpm to smooth and fix the coating film, Leave it for about 5 minutes at room temperature to dry, hold it at about 120 ° C for about 20 minutes, then raise it to about 175 ° C for about 10 minutes, and then keep it for about 30 minutes, then the second layer film. Got

When the refractive index and the film thickness of the second layer film were measured in the same manner as the first layer film, the refractive index was about 1.44 and the film thickness was about 2 μm.
It was a m ₂ SiO ₂ -based thin film. The following items were evaluated for the obtained tempered glass with a two-layer film. [Optical characteristics]: Spectrophotometer (U4000, manufactured by Hitachi, Ltd.)
Measure the transmittance between 340 and 1800 nm with JIS Z 8722
And visible light transmittance Tv according to JIS R 3106 or JIS Z 8701
(%) (380-780nm), UV transmittance Tu according to ISO 9050
v (%) (282.5 to 377.5 nm), stimulus purity (%), color tone, etc. were determined. [Degree of haze]: Haze value H was determined according to JIS K6714. 3% or less for architectural use, 1% for automotive use
% Or less was accepted. [Electromagnetic wave transmission]: Reflection loss value (d
B) is compared with a normal 3mm clear glass (FL3t) single plate product. An absolute value (△ dB) of the difference was considered to be within 2 dB. [Chemical resistance]: Acid resistance: Immersed in 1N hydrochloric acid at room temperature for 6 hours.

Alkali resistance: Immersed in a 1N caustic soda aqueous solution at room temperature for 6 hours. After each test, the appearance was visually evaluated and the change in transmittance at 370 nm was examined. [Heat resistance]: After boiling in boiling water at 100 ° C. for about 6 hours, except for 10 mm around the periphery, there was no abnormality such as generation of bubbles, clouding, or cracking of glass, and the result was passed. [Also called boiling resistance] [Moisture resistance]: After leaving for 2 weeks in a controlled condition of 50 ± 2 ° C and relative humidity of 95 ± 4%, there should be no abnormalities such as foaming, clouding, and glass cracking. I passed. [Electrical characteristics]: Mitsubishi Yuka surface high resistance meter (HIRESTA HT
-210).

(Sheet resistance value) (M Ω / port). 10MΩ /
Passed by mouth. [Abrasion resistance]: Taber abrasion tester (wear wheel CS-10F, load 500 gf, 1000 rotations) in accordance with JIS R 3212 and JIS R 3221.

As a result, the visible light transmittance Tv is about 90%,
Ultraviolet transmittance Tuv is about 9.5%, reflection stimulus purity Pe is 1
%, The transmitted and reflected colors of the laminated thin film due to the D ₆₅ light source are neutral tones and there is no glare due to reflection, and the ultraviolet transmittance of ordinary green tone glass (3.5 mm thickness) is about 30%. In comparison, the visible light transmittance was high, and the ultraviolet light transmittance was significantly reduced.

Further, the haze value H was about 0.3%, the haze value ΔH by the Taber test was about 4.5%, and no change was observed in the appearance and ultraviolet transmittance after the acid resistance and alkali resistance tests. It was

In addition to the sufficiently excellent ultraviolet shielding property,
It has a high surface resistivity, which is similar to that of single glass, such as 80MHz (FM
(Radio wave band), about 520 to 1630 KHz (AM radio wave band), etc., in particular, shows the same radio wave transmission as ordinary single plate glass, and also has sufficiently stable and excellent adhesiveness, heat resistance, and moisture resistance, and both pass. It has excellent habitability, is environmentally friendly and highly safe, and can comfortably receive various radio waves including the AM band. It can be fully adopted as a single glass plate for building window glass, etc., and is also used for automobile window glass. It was possible to fully meet expectations, such as possible.

In addition, when various other characteristics such as weather resistance (eg, about 1000 hours with a Sunshear weather meter: visible light transmittance is almost unchanged) were evaluated, all of them passed. there were.

Example 2 On the same glass substrate as in Example 1, zinc oxide fine particle-containing silica binder [ZnO / SiO ₂ = about 52/48 weight ratio; ZnO
Average particle size of about 2 to 4 nm: Sumitomo Osaka Cement Co., Ltd.] is diluted with hexylene glycol as a diluent so that the solid content concentration is about 10.5% by weight, and the viscosity is 20 cP. Coating solution on the glass substrate by a flexographic printing method, dried at about 300 ° C for about 30 minutes, then baked in an electric furnace at about 620 ° C for about 5 minutes, and then strengthened by cooling with air. Glass with a layer film was produced.

When the refractive index and the film thickness of the first layer film were measured in the same manner as in Example 1, the refractive index was about 1.60 and the film thickness was about 900 n.
It was a ZnO-SiO ₂ based thin film of m ₂ . Subsequently, the tempered glass substrate having one side coated with the film was masked by dip coating with the silicone-based hard coating film solution prepared as described above in the proportions shown in Table 1, after being dipped in a dip tank, Pull up at about 10 mm / sec, leave at room temperature for about 30 minutes to dry, hold at about 120 ° C for about 20 minutes, raise to about 175 ° C for about 10 minutes, then hold for about 30 minutes Then, a second layer film was obtained.

When the refractive index and the film thickness of the second layer film were measured in the same manner as in Example 1, the refractive index was about 1.44 and the film thickness was about 2.2.
It was a SiO ₂ thin film of μm. Each item of the obtained glass with a two-layer film was evaluated in the same manner as in Example 1.

[0069] As a result, Tv is about 85% Tuv together show a similar excellent optical property and about 8%, etc. Example 1, reflecting excitation purity Pe is not more than about 1%, the laminated thin film by illuminant D ₆₅ Neutral tones and no glare due to reflection, and the visible color is higher than that of ordinary green tint glass (3.5 mm thick) similar to that of Example 1 of about 30%. Also in terms of light transmittance, the UV transmittance could be considerably reduced.

Further, the haze value H was about 0.2%, the haze value ΔH by the Taber test was about 3.3%, and the appearance and the ultraviolet transmittance after the acid resistance and alkali resistance test were changed in Example 1. Was not recognized as well.

Further, in the same manner as in Example 1, in addition to the sufficiently excellent optical properties such as ultraviolet ray shielding property, the high surface resistivity shows the radio wave transmission equivalent to that of the ordinary single glass, and the sufficiently stable and excellent adhesion. It has excellent habitability, is environmentally friendly and highly safe, and can comfortably receive various radio waves including the AM band, and is a window glass for construction as a single plate glass. It was possible to fully meet the expectations, such as being able to be adopted sufficiently in such things as being applicable to window glass for automobiles. In addition, when various characteristics such as the weather resistance were evaluated, all of them passed.

Example 3 On the same glass substrate as in Example 1, the same first layer film as in Example 1 was applied on the same substrate as in Example 1 to form a film. The first
When the refractive index and the film thickness of the layer film were measured in the same manner as in Example 1, the film was a ZnO—SiO ₂ thin film having a refractive index n ₂ = 1.65 and a film thickness t ₂ = 375 nm.

Then, the above-prepared silicon-based hard coating film solution was prepared by dip coating at the ratio shown in Table 1 by a dip coating method. After about 15mm / se
Pull up with c, leave at room temperature for about 30 minutes to dry,
Hold at about 120 ° C for about 20 minutes, then about 10 minutes at about 175 ° C
After the temperature was raised to, the temperature was maintained for about 30 minutes to obtain a second layer film.

When the refractive index and the film thickness of the second layer film were measured in the same manner as in Example 1, the refractive index was about 1.44 and the film thickness was about 3.0.
It was a SiO ₂ thin film of μm. Each item of the obtained glass with a two-layer film was evaluated in the same manner as in Example 1.

[0075] As a result, Tv is about 88% Tuv together exhibit similarly good optical properties and is about 8.5%, etc. Example 1, reflecting excitation purity Pe is not more than about 1%, the laminated thin film by illuminant D ₆₅ The transmission color and the reflection color of the same are neutral color tones, and there is no glare due to reflection.
Compared with a Tv of about 81% and an ultraviolet transmittance of about 30% for tinted glass (3.5 mm thickness), the ultraviolet transmittance could be significantly reduced even with a high light transmittance.

Further, the haze value H was about 0.2%, the haze value ΔH by the Taber test was about 4.9%, and the appearance and the ultraviolet transmittance after the acid resistance and alkali resistance test were changed in Example 1. Was not recognized as well.

Further, in the same manner as in Example 1, in addition to a sufficiently excellent ultraviolet ray shielding property, it exhibits a radio wave transmission equivalent to that of a normal single plate glass with a high surface resistivity, and has sufficiently stable and excellent adhesiveness and heat resistance. It also shows moisture resistance and both pass,
It has excellent habitability, is environmentally friendly, has high safety, and can comfortably receive various radio waves including the AM band. It can be sufficiently adopted as a single plate glass for building window glass, etc., and can also be used for automobile window glass. I was able to fully meet my expectations. In addition, when various characteristics such as the weather resistance were evaluated, all of them passed.

Comparative Example 1 On the same glass substrate as in Example 1, zinc oxide fine particle-containing silica binder [ZnO / SiO ₂ = about 70/30 weight ratio] was added to isobutyl acetate so that the solid content concentration was about 20 weight%. A coating solution for an ultraviolet absorbing film having a viscosity of about 2 cP is obtained by diluting a mixed solvent of an ester compound such as and a high boiling point alcohol compound such as butanol as a diluting solvent, and a dip coating method is used. After dipping the glass substrate with one side of the film pasted and masked in a dip tank,
It is pulled up at about 15 mm / sec, left at room temperature for about 10 minutes, dried at about 200 ° C for about 30 minutes, and baked in an electric furnace at about 620 ° C for about 5 minutes to strengthen with air cooling. A tempered glass with a layer film was obtained.

The refractive index and the film thickness of the obtained glass with a two-layer film were measured in the same manner as in Example 1. The refractive index was 1.68 and the film thickness was about 1500 nm. The entire surface of the laminated film was cracked. Was observed.

Comparative Example 2 In the same manner as in Example 1, the same first layer film as in Example 1 was applied and formed on the same glass substrate as in Example 1. The first
When the refractive index and the film thickness of the layer film were measured in the same manner as in Example 1, the film was a ZnO—SiO ₂ thin film having a refractive index of 1.66 and a film thickness of 750 nm.

Then, a silicon-based hard coating solution shown in Table 1 was formed on the first layer film by a spin coat method in the same manner as in Example 1 to form a second layer film. When the refractive index and the film thickness of the second layer film were measured in the same manner as in Example 1, the film was a SiO ₂ thin film having a refractive index of 1.44 and a film thickness of 1.8 μm.

Each item of the obtained double-layered glass was evaluated in the same manner as in Example 1. As a result, Tv is about 90%
, Tuv of about 10%, reflection stimulus purity Pe of about 1% or less, and haze value of H of about 0.3% showed excellent optical characteristics as in Example 1, but the adhesion was insufficient. In the Taber test, the second layer film was easily peeled off, and the heat resistance was unacceptable in terms of durability such as adhesion of the second layer film.

Comparative Example 3 In the same manner as in Example 1, the same first layer film as in Example 1 was applied and formed on the same glass substrate as in Example 1. The first
When the refractive index and the film thickness of the layer film were measured in the same manner as in Example 1, the film was a ZnO—SiO ₂ thin film having a refractive index of 1.67 and a film thickness of 850 nm.

Then, a silicon-based hard coating solution shown in Table 1 was formed on the first layer film by a spin coat method at a high speed of about 400 rotations in the same manner as in Example 1. The second layer film was used. When the refractive index and the film thickness of the second layer film were measured in the same manner as in Example 1, the refractive index was 1.44 and the film thickness was 0.5 μm.
Was a SiO ₂ thin film.

Each item of the obtained double-layered glass was evaluated in the same manner as in Example 1. As a result, Tv is about 90%
The degree of Tuv was about 12%, and the reflection stimulus purity Pe was about 15%. The interference optics and glare were strong, and the optical characteristics were insufficient. Further, in the Taber test, the second layer film was easily worn away and the first layer film was exposed. Furthermore, the chemical resistance also showed a significant decrease in the ultraviolet absorption power, and the durability was unacceptable.

[0086]

[Table 1]

[0087]

As described above, according to the present invention,
Gives various types of glass exceptional UV blocking properties that are friendly to the environment and people, eliminates the poor durability and difficulty of optical design that accompany conventional ZnO films, and makes full use of its advantages, and has a haze value. It is extremely low and provides a good balance of transparency and prevention of glare and reflection, and can reduce reception obstacles in various broadcasts, with the same radio wave transmission performance as ordinary float glass. Without deteriorating the reception performance of the glass antenna, it is possible to reduce the radio wave interference such as the ghost phenomenon, a comfortable environment can be secured inside and outside the vehicle, and the color tone of the glass substrate is almost maintained. It is possible to obtain a useful UV-shielding glass and its manufacturing method that can be applied to not only a single plate as a building window material but also an automobile window material, etc., because of its excellent wear resistance and chemical resistance. It is provided easily.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09K 3/00 104 C09K 3/00 104A E06B 5/18 E06B 5/18 (72) Inventor Shinkawa Masahiro 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Glass Research Institute

Claims (10)

[Claims] 1. A Zn having a refractive index n ₁ of 1.5 to 1.8 and a film thickness t ₁ of 1.5 μm or less as a first layer on the surface of a glass substrate.
An O-SiO ₂ thin film is formed on the first layer as a second layer having a refractive index n ₂ of 1.4 to 1.5 and a film thickness t ₂ of 1 μm or more. An ultraviolet-shielding glass, which is formed by coating and laminating a film. 2. The ultraviolet shielding glass according to claim 1, wherein the ZnO—SiO ₂ thin film is formed from a solution containing zinc oxide fine particle silica binder as a main component. 3. The silicon-based hard coating film as R ¹ _n Si (OR ² ) ₃ , R ³ Si (OR ⁴ ) ₃ , Si (OR ⁵ ) ₄ [R ¹ :
Epoxy-containing alkyl group, R ² , R ³ , R ⁴ , R ⁵ : Alkyl group] is used as the main component of an epoxy group-containing organosiloxane prepolymer obtained by hydrolysis partial condensate of an alkoxysilane compound 3. The ultraviolet shielding glass according to claim 1, which is formed by forming a film from the above solution. 4. The silicon-based hard coating film is formed from a solution containing a benzophenone-based ultraviolet absorber in a silicone-based hard coating film solution. The ultraviolet shielding glass according to claim 1. 5. On the surface of a glass substrate, first as a first layer
Apply ZnO-SiO ₂ thin film solution at room temperature ~ 300 ℃ 0.5 ~
After drying for 60 minutes, bake at 400-700 ° C for 0.1-30 minutes to form a ZnO-SiO ₂ thin film so that the refractive index n ₁ is 1.5-1.8 and the film thickness t ₁ is 1.5 μm or less. Then, a silicone-based hard coating film solution is applied as a second layer on the first layer, dried at room temperature to 100 ° C. for 0.5 to 30 minutes, and then at 150 to 300 ° C. at 0.5. A UV-shielding glass, which is heat-cured for about 60 minutes and has a refractive index n ₂ of 1.4 to 1.5 and a film thickness t ₂ of 1 μm or more, which is coated and laminated to form a silicone-based hard coating film. Manufacturing method. 6. The method for producing an ultraviolet shielding glass according to claim 5, wherein the ZnO—SiO ₂ thin film solution is a solution containing zinc oxide fine particle silica binder as a main component. 7. The solution for a silicon-based hard coating film is R ¹ _n Si (OR ² ) ₃ , R ³ Si (OR ⁴ ) ₃ , Si (OR ⁵ ) ₄ [R ¹ :
Epoxy-containing alkyl group, R ² , R ³ , R ⁴ , R ⁵ : Alkyl group] is used as the main component of an epoxy group-containing organosiloxane prepolymer obtained by hydrolysis partial condensate of an alkoxysilane compound 7. The method for producing an ultraviolet shielding glass according to claim 5, which is a solution obtained by 8. The silicone-based hard coating film solution is a solution containing a benzophenone-based ultraviolet absorber in the silicone-based hard coating film solution. 5. The method for producing an ultraviolet shielding glass as described in 5 to 7. 9. The method for applying the solution for the first layer is spin coating method, dip coating method, reversal coating method, flexographic printing method, and the second coating method.
As a method for applying the layer solution, a spin coat method,
9. The method for producing an ultraviolet shielding glass according to claim 5, which is carried out by a dip coating method or a spray coating method. 10. The firing of the ZnO—SiO ₂ based coating film as the first layer is performed simultaneously with the step of heat bending treatment and / or heat strengthening treatment of the glass substrate.
10. The method for manufacturing the ultraviolet shielding glass described in 9 above.