JPH0797535A - Ultraviolet-screening glass and its production - Google Patents

Abstract

PURPOSE:To produce an ultraviolet-screening glass suitable for window glass for an automobile or a building, having a wide acceptable range of firing time and firing temperature and excellent in scuffing resistance, abrasion resistance and one or more properties among formability and acid resistance and to provide its production method. CONSTITUTION:The ultraviolet-screening glass 50 is composed of an undercoating film 14 made of SiO2, having 0.05 to 0.6mum thickness and formed on a glass base 12, an ultraviolet-screening film 16 made from a fine powder of zinc oxide having <=0.1mum particle diameter and amorphous SiO2 with a weight ratio of SiO2/ZnO=0.25 to 0.67, having 0.2 to 1.5mum thickness and formed on the undercoating film 14 and a protective film 18 made of amorphous SiO2, having 0.1-to 0.6mum thickness and formed on the ultraviolet-screening film 16.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for window glass for automobiles and buildings, has a wide allowable range of firing temperature and firing time, is excellent in at least one of moldability and acid resistance, and is resistant to The present invention relates to an ultraviolet blocking glass having excellent scratch resistance and abrasion resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Generally, as a method for producing an ultraviolet blocking glass, a method of using a glass composition, a method of sticking a transparent film in which an organic ultraviolet absorber is kneaded on a plate glass,
Also, a method of forming a transparent ultraviolet blocking film on a plate glass is known.

In the above method, the glass composition is a glass composition in which cerium oxide, titanium oxide, iron oxide, vanadium oxide or the like is added to ordinary glass to absorb ultraviolet rays. Since it is a special glass composition, there are disadvantages that the manufacturing cost is high, and that it is difficult to make the composition uniform and the ultraviolet absorbing performance is unstable. The method of sticking a transparent film on a plate glass has a problem in durability of the organic ultraviolet absorber and is not practical because the film strength is weak. In order to solve this problem, a method of sandwiching the above film between two plate glasses to form a laminated glass is conceivable, but it is too costly, and therefore, the windshield of an automobile and some architectural windows where safety is important. The reality is that it is only used for glass.

As a method of forming an ultraviolet blocking film on a plate glass, a hydrolyzate of Ti-alkoxide and Si-alkoxide is alternately coated and baked to form TiO ₂ --Si.
Method of forming O ₂ multilayer film, method of oxidatively pyrolyzing an ultraviolet-absorbing organometallic compound such as zinc, ZnO, TiO 2
₂ , there is a method of applying a paint in which powder such as CeO is dispersed. However, the method of forming a TiO ₂ —SiO ₂ multilayer film requires a multilayer film of 5 to 10 layers whose film thickness is accurately controlled, which is disadvantageous in that manufacturing costs and time. In addition, it is difficult to obtain a uniform and clean film by the thermal decomposition method, and the film thickness cannot be increased, so that the ultraviolet absorption performance is inferior. In addition, ZnO, TiO ₂ , C
The method using a coating material in which a fine powder such as eO is dispersed can obtain the ultraviolet absorbing film most easily, but has a problem that the coating film hardness is weak. Furthermore, for applications requiring scratch resistance and abrasion resistance, such as window glass for automobiles and buildings, the ultraviolet blocking films obtained by the above-mentioned methods have insufficient film hardness. There is a problem that it is not suitable.

In order to solve such a problem, the inventors of the present invention applied a coating material in which fine powder of zinc oxide is dispersed to a fine powder of zinc oxide having a particle diameter of 0.1 μm or less. SiO ₂ / Zn in siloxane solution
O = 0.25 to 0.67 (weight ratio) were mixed, and the dispersion obtained by dispersing the above zinc oxide fine powder was 0.2 to 1.5 μm in dry film thickness. The glass substrate to 580-7
By baking at 00 ° C to form an ultraviolet blocking film,
An ultraviolet blocking glass having excellent scratch resistance and abrasion resistance is obtained (Japanese Patent Application No. 4-294674).

[0006]

By the way, when the ultraviolet blocking glass obtained by such a manufacturing method is used for window glass for automobiles, the self-weight bending method, pressing method, gas furnace method, new gravity method, etc. Need to be molded. However, since the ultraviolet blocking glass obtained by the above-mentioned manufacturing method is abnormally deformed during heating during molding, the ultraviolet blocking glass may be broken in the carrying step and the quenching / strengthening step. Further, the ultraviolet blocking glass that can be molded also has a defect that defects such as glass breakage during storage, defective dimensions, and surface distortion occur.

The inventor of the present application has found that the defective molding occurs in the molding process of the window glass for automobiles using the ultraviolet blocking glass, although the heating time is as short as several minutes to less than 10 minutes, but the glass surface temperature is 710 to 750 ° C. The temperature is extremely high, and the firing temperature range of the UV blocking film of the UV blocking glass is 580 to 7
It was concluded that the temperature was higher than 00 ° C.
That is, at a high temperature of 710 to 750 ° C., the glass substrate is softened, and the glass substrate is largely deformed toward the ultraviolet blocking film side due to the difference in thermal expansion coefficient between the ultraviolet blocking film and the glass substrate. Usually, in order to secure the designed shape in the molding step, when a glass substrate of 300 mm square is used, for example, it is necessary that the amount of warpage after processing for 10 minutes at a firing temperature range of 710 to 750 ° C. is 1 mm or less. .

Further, according to the method for producing an ultraviolet blocking glass disclosed in Japanese Patent Application No. 4-294674, the dispersion is preferably fired at a temperature of 580 to 700 ° C., and the firing time is 10 minutes to 60 minutes. The following are preferred, but 640
In the case of firing for a long time in firing at a temperature of not lower than 0 ° C., zinc oxide may react with SiO ₂ in the organopolysiloxane of the binder to be vitrified, and the ultraviolet absorbing power may be lost. Further, when the material forming the glass substrate is soda-lime glass, zinc oxide may react with SiO ₂ in the glass substrate to be vitrified, and the ultraviolet absorbing power may be lost. This is because the ultraviolet absorption of zinc oxide is due to the semiconductivity due to the crystal structure, that is, the energy gap between the conduction band and the valence band, and the ultraviolet absorption is lost when the crystal structure collapses. On the other hand, in order to make the ultraviolet blocking film have a surface hardness and abrasion resistance that are practically unproblematic as a window glass for automobiles or buildings, it is necessary to burn at a temperature as high as possible to make the organopolysiloxane inorganic. is there. That is, the lower limit of firing temperature and firing time is determined by the mineralization of organopolysiloxane, that is, abrasion resistance, while the higher limit of firing temperature and firing time is the vitrification of zinc oxide. , I.e., it is determined by UV absorption. Therefore, in order to satisfy the ultraviolet absorbing power, the surface hardness and the abrasion resistance, the firing temperature and the firing time must be controlled within a very narrow range, and there is a problem that the production is difficult.

Further, the ultraviolet-shielding glass obtained by the method for producing the ultraviolet-shielding glass disclosed in Japanese Patent Application No. 4-294674 has insufficient acid resistance and is used for window glass for automobiles or buildings. However, there was a risk that the ultraviolet blocking film would deteriorate due to acid rain or exhaust gas. that is,
Zinc oxide in the UV blocking film dissolves easily in acid, so if liquid in which exhaust gas is dissolved or acid rain comes into contact with the UV blocking film, zinc oxide dissolves and the UV blocking film becomes cloudy or Had a possibility that the zinc oxide was completely dissolved and the ultraviolet absorbing power was lost.

The present invention has been made in view of the above circumstances, has a wide allowable range of firing temperature and firing time, is excellent in at least one of moldability and acid resistance, and has scratch resistance and abrasion resistance. An object of the present invention is to provide an ultraviolet blocking glass having excellent properties and a method for producing the same.

[0011]

Therefore, the inventors of the present invention have made earnest studies on an ultraviolet blocking glass which is excellent not only in scratch resistance and abrasion resistance but also in moldability and a method for producing the same. The inventors have found that the moldability can be improved by selecting the thickness and the firing temperature, and by further forming the ultraviolet blocking films on both surfaces of the glass substrate, the present invention has been completed. That is, in the method for producing an ultraviolet blocking glass according to claim 2 of the present invention, zinc oxide fine powder having a particle size of 0.1 µm or less is added to an organopolysiloxane solution to be SiO ₂ / Zn.
O = 0.25 to 0.67 (weight ratio) were mixed to obtain a dispersion liquid obtained by dispersing the zinc oxide fine powder, and a dry film thickness of 0.2 to 1.0 µm was obtained. After coating one surface of the glass substrate to a thickness,
Forming an ultraviolet blocking film by baking at 0 to 700 ° C.,
Further, in the method for producing an ultraviolet blocking glass according to claim 4, the dispersion is applied to both surfaces of a glass substrate so that the dry film thickness is 0.1 to 1.2 μm, and then the glass is obtained. The baking of the substrate at 520 to 700 ° C. to form the ultraviolet blocking film was the means for solving the above problems.

Further, the inventors of the present invention have found that zinc oxide fine powder is used as SiO ₂ in an organopolysiloxane or a glass substrate.
When the glass substrate is made of soda lime or the like, the Na component in the glass substrate is ion-diffused into the ultraviolet blocking film during high temperature firing when the glass substrate is made of soda lime or the like. Then, it was determined that it promotes vitrification of the zinc oxide fine powder. That is,
It is the firing temperature and Na ions that determine the vitrification rate of zinc oxide, and by suppressing the diffusion of Na ions into the ultraviolet blocking film, it is possible to raise the upper limit of the firing temperature. I found it possible. Then, as a result of studying a method of suppressing diffusion of Na ions into the organopolysiloxane in the glass substrate, it was found that forming an undercoat film between the glass substrate and the ultraviolet blocking film is effective. Came to. That is, in the method for producing an ultraviolet blocking glass according to claim 6 of the present invention, the film thickness of the organopolysiloxane when dried is 0.
After coating on a glass substrate so as to have a thickness of 05 to 0.6 μm, the glass substrate is baked at 120 to 700 ° C. to form an undercoat film, and then the dispersion is dried to a film thickness of 0.2 to After coating the undercoat film to a thickness of 1.5 μm, the glass substrate is coated with 520 to 700.
Forming an ultraviolet blocking film by firing at ° C was used as a means for solving the above problems.

Further, the inventors of the present invention have earnestly studied not only scratch resistance and abrasion resistance but also excellent acid resistance of the ultraviolet blocking glass and a method for producing the same. As a result, a protective film is formed on the ultraviolet blocking film. As a result, they have found that the acid resistance can be improved, and have reached the present invention. That is, in the method for producing an ultraviolet blocking glass according to claim 8 of the present invention, the dispersion is applied onto a glass substrate so as to have a dry film thickness of 0.2 to 1.5 μm, 12 glass substrates
The film is baked at 0 to 700 ° C. to form an ultraviolet blocking film, and then the organopolysiloxane is dried to a film thickness of 0.1 to 0.
After coating on the ultraviolet blocking film to have a thickness of 6 μm,
Forming a protective film by baking the glass substrate at 520 to 700 ° C. was a means for solving the above problems.

Further, the inventors of the present invention have not only scratch resistance and abrasion resistance, but also can raise the limit value on the high temperature side of the firing temperature, and have excellent acid resistance, and a UV blocking glass and a method for producing the same. As a result of diligent study, the undercoat film is formed between the glass substrate and the ultraviolet blocking film, and a protective film is further formed on the ultraviolet blocking film, whereby the upper limit of the firing temperature can be increased. Is possible,
Moreover, they have found that the acid resistance can be improved, and have reached the present invention. That is, in the method for producing an ultraviolet blocking glass according to claim 10 of the present invention, an undercoat film is formed in the same manner as in the method for producing an ultraviolet blocking glass according to claim 6, and then the ultraviolet blocking glass according to claim 8 is formed. The formation of the protective film after forming the ultraviolet blocking film in the same manner as in the manufacturing method was the means for solving the above problems.

The present invention will be described in detail below. First, the ultraviolet blocking glass according to claim 1 will be described. Figure 1
FIG. 3 is a schematic configuration diagram showing an example of the ultraviolet blocking glass (hereinafter, abbreviated as first ultraviolet blocking glass) according to claim 1, and reference numeral 10 in FIG. 1 denotes the first ultraviolet blocking glass.
The first ultraviolet blocking glass 10 is formed by forming an ultraviolet blocking film 16 on one surface of a glass substrate 12, and the ultraviolet blocking film 16 is a zinc oxide fine powder having a particle size of 0.1 μm or less and an amorphous material. Composed of SiO ₂ , SiO ₂ / ZnO =
The ratio is 0.25 to 0.67 (weight ratio), and the thickness is 0.2 to 1.0 μm.

To manufacture such a first ultraviolet blocking glass 10, first, zinc oxide fine powder is mixed and dispersed in an organopolysiloxane solution to prepare a dispersion liquid. As the above zinc oxide fine powder, it is preferable to use one having a particle size of 0.1 μm or less. The zinc oxide fine powder having a particle diameter of 0.1 μm is used because a dispersion film made of a dispersion liquid of an inorganic powder generally has a dispersed particle diameter of 1 / wavelength of visible light.
It is known that when it is less than 2, that is, 0.2 μm, it becomes transparent, and when it is 1/4 or less of the wavelength of visible light, that is, it becomes almost transparent at 0.1 μm or less, and therefore the particles of the zinc oxide fine powder to be used The smaller the diameter, the better the transparency of the dispersion film.
It is preferable to use zinc oxide fine powder of m or less. Also,
Zinc oxide in such powder state is usually agglomerated, and especially those with a small particle size have a strong cohesive force and are difficult to disperse.
To disperse the hard agglomerated particles to 0.1 μm or less,
As will be described later, the surface of the particles may be wetted with a solvent having an affinity for zinc oxide, the mechanical energy stronger than the cohesive force between the zinc oxide fine powder particles may be applied to separate the particles, and the dispersion may be further stabilized.

The above-mentioned organopolysiloxane is not particularly limited in terms of production method, molecular weight, molecular structure, etc., as long as an organic component is decomposed and dissociated after heating and finally becomes an amorphous SiO ₂ film. . Such an organopolysiloxane can be obtained, for example, by reacting a monofunctional to tetrafunctional organochlorosilane or alkoxysilane with water to obtain silanol, and then performing a condensation reaction in an acid solvent. Further, this organopolysiloxane is dissolved in a solvent in advance and used as a solution. The solvent for dissolving the organopolysiloxane needs to have an affinity with zinc oxide, and specifically, alcohol-based or ester-based polar organic solvents are suitable. However, it is possible to increase the affinity (wettability) with zinc oxide by adding a surfactant or modifying the surface of zinc oxide particles with a fatty acid, etc., so use a non-polar solution or water. You can Regarding the selection of such a solvent, in addition to the wettability with zinc oxide as described above, there are conditions such as solubility, viscosity, evaporation rate and price of the organopolysiloxane. It is also possible to use a combination of 5 kinds of solvents.

When the zinc oxide fine powder is mixed with the organopolysiloxane solution to prepare a dispersion, SiO ₂ in the organopolysiloxane and Zn which is the zinc oxide powder are mixed.
The weight ratio (SiO ₂ / ZnO) with respect to O is 0.25 or more.
It is prepared and blended so as to be in the range of 67 or less. That is, when the weight ratio is less than 0.25, the dispersion of the zinc oxide fine powder is deteriorated and the dispersion liquid cannot be formed into a film.
This is because even if the dispersion liquid can be prepared, the transparency of the obtained ultraviolet blocking film becomes insufficient because the refractive index thereof becomes large.
On the other hand, if the weight ratio exceeds 0.67, the ultraviolet ray absorbing performance of the obtained ultraviolet ray blocking film is deteriorated, and further, fine cracks may occur in the ultraviolet ray blocking film formed in the subsequent high temperature baking step. .

To add zinc oxide fine powder to the organopolysiloxane solution and disperse the fine powder, since the strongly agglomerated particles (fine powder) are separated as described above, the cohesive energy of the zinc oxide fine powder is larger than that of the zinc oxide fine powder. A disperser capable of providing energy is used. However, the form is not particularly limited, and specifically, a sand mill, an attritor, a ball mill, a roll mill, a homogenizer, an ultrasonic disperser or the like can be used alone or in combination. Furthermore, in order to stabilize the dispersion state of the zinc oxide fine powder dispersed by the disperser, for example, a method of causing steric hindrance due to polymer adsorption, a method of repulsive force of adsorbed ions, a method of using a coupling agent, etc. It can also be adopted.

Next, the dispersion liquid thus prepared is applied to one surface of the glass substrate 12. Although soda lime glass is preferably used as the glass substrate 12 here, hard glass or quartz glass may be used, and the material thereof is not particularly limited. As a method for applying the dispersion liquid to the glass substrate 12, each coating method such as spray coating, roll coating, dip coating, flow coating, and spin coating can be adopted. Regarding the coating amount of the above-mentioned dispersion liquid, the film thickness after drying obtained in the subsequent baking step is 0.2 μm.
It is applied so as to have a thickness of 1.0 μm or less. This is because if the obtained film thickness is less than 0.2 μm, the ultraviolet ray transmittance becomes large, for example, 15% or more at 360 nm, and the effect of blocking the ultraviolet rays becomes low. On the other hand, when the amount of coating exceeds 1.0 μm, there is no problem in the subsequent firing step, but abnormal deformation occurs during heating during molding as automobile glass, and glass cracks, dimensional defects, surface distortion, etc. This is because a defect will occur.

Next, the glass substrate 12 coated with the dispersion liquid.
Is baked at 520 to 700 ° C. to form the ultraviolet blocking film 16 on one surface of the glass substrate 12. Here, the firing temperature of the dispersion liquid is set to 520 ° C. or more and 700 ° C. or less, because when the temperature is lower than 520 ° C., the thermal decomposition of the organopolysiloxane is insufficient and it does not become inorganic SiO ₂ and a high hardness ultraviolet blocking film 16 is obtained. This is because it cannot be applied to applications requiring high scratch resistance and abrasion resistance such as automobiles and window glass for construction. On the other hand, when the temperature exceeds 700 ° C., when the glass substrate 12 is made of soda-lime glass that is generally used for window glass for automobiles, Na component in the glass substrate 12 diffuses into the ultraviolet blocking film 16 to form zinc oxide. It has a high vitrification rate and may lose its ultraviolet absorbing power.

By the way, in the method for producing an ultraviolet blocking glass described in Japanese Patent Application No. 4-29467, the firing temperature range is 5
Although 80 to 700 ° C. is adopted, as a result of examining the relationship between the firing temperature (° C.) and the haze change (%) after that, it was found that
It was confirmed that a high-hardness ultraviolet blocking film was obtained even in the firing temperature range of 0 to 700 ° C., and that scratch resistance and abrasion resistance were practically sufficient. FIG. 2 shows the relationship between the firing temperature (° C.), the firing time (minutes) and the haze change [ΔH (%)]. Here, the required abrasion resistance of the ultraviolet blocking glass is evaluated by the Taber type abrasion resistance test (wear wheel CS-10F, 500 g load,
If the haze change before and after 1000 rotations is within 4%,
If the firing temperature is lower than 520 ° C, the haze change exceeds 4% even if the firing time is lengthened. On the other hand, if the firing temperature is 520 ° C or higher, the haze change can be controlled to 4% or less by controlling the firing time. is there. Therefore, as the firing temperature of the present invention, 520 ° C. was set as the minimum firing temperature.

The firing time, that is, the glass substrate 12
Is preferably maintained at 10 to 120 minutes depending on the firing temperature. When the temperature is low within the baking temperature range, long-time baking is required, and when the temperature is high, the ultraviolet blocking film 1 having high hardness in a short time 1
6 can be obtained, and an ultraviolet blocking glass having excellent scratch resistance and abrasion resistance can be obtained. Here, if the firing time is less than 10 minutes, the inorganic polyorganosiloxane is not sufficiently mineralized to obtain a UV blocking film having good scratch resistance, while the hardness of the UV blocking film is not improved even if heated for more than 120 minutes. This is because the vitrification of zinc oxide is promoted and the ultraviolet absorption performance of the ultraviolet blocking film 16 formed may be deteriorated. Cooling of the fired glass may be either slow cooling or rapid cooling. If it is slowly cooled, it becomes a normal plate glass, while if it is rapidly cooled, it becomes a tempered glass. It is also possible to mold in a softened state, and these steps do not affect the performance of the ultraviolet blocking film. The first ultraviolet blocking glass 10 thus obtained has excellent scratch resistance and abrasion resistance, and excellent moldability.

Next, the ultraviolet blocking glass according to claim 3 of the present invention will be described. FIG. 3 is a schematic configuration diagram showing an example of the ultraviolet blocking glass (hereinafter, abbreviated as second ultraviolet blocking glass) according to claim 3, and reference numeral 20 in FIG.
Is a second UV blocking glass. The second ultraviolet blocking glass 20 is different from the first ultraviolet blocking glass 10 shown in FIG. 1 in that ultraviolet blocking films 16 and 16 are formed on both surfaces of a glass substrate 12, and the thickness of each ultraviolet blocking film is different. Is 0.1 to 1.2 μm.

In order to manufacture such a second UV blocking glass 20, the dispersion has a dry film thickness of 0.1 to 1.2 μm.
The method may be the same as the method for manufacturing the first ultraviolet blocking glass 10 described above, except that the both surfaces of the glass substrate 12 are applied so as to have the above thickness. Here, the dry film thickness of the dispersion is set to 0.
The ultraviolet blocking film 1 has a thickness of 1 μm or more and 1.2 μm or less.
Since 6 is formed on both sides of the glass substrate 12, even if each thickness is 0.1 μm, an ultraviolet blocking effect equivalent to 0.2 μm can be obtained, and conversely 0.1 μm.
If it is less than the above range, the ultraviolet ray transmittance is increased and the ultraviolet ray shielding effect is lowered. Further, even if the glass substrate is deformed, since it acts on both sides of the glass substrate 12, there is no problem unless it exceeds 1.2 μm, and conversely 1.2 μm.
If you apply more than the above, there will be no problem in the subsequent firing process,
This is because abnormal deformation occurs during heating during molding as glass for automobiles, and defects such as glass cracks, dimensional defects, and surface distortion occur. The second ultraviolet blocking glass 20 thus obtained has excellent scratch resistance and abrasion resistance, and also has excellent moldability.

Next, the ultraviolet blocking glass according to claim 5 of the present invention will be described. FIG. 4 is a schematic configuration diagram showing an example of the ultraviolet blocking glass (hereinafter, abbreviated as third ultraviolet blocking glass) according to claim 5, and reference numeral 30 in FIG.
Is a third UV blocking glass. The third ultraviolet blocking glass 30 differs from the first ultraviolet blocking glass 10 shown in FIG. 1 in that it is made of SiO ₂ and has a thickness of 0.05 between the glass substrate 12 and the ultraviolet blocking film 16. ~ 0.
The undercoat film 14 having a thickness of 6 μm is formed, and the ultraviolet blocking film 16 has a thickness of 0.2 to 1.5 μm. The SiO ₂ forming the undercoat film 14 may be crystalline or amorphous.

In order to manufacture such a third ultraviolet blocking glass 30, first, the organopolysiloxane for forming the undercoat film has a thickness of 0.05 to 0.6 μm when dried.
After that, the glass substrate 12 is coated on the glass substrate 12 at a temperature of 120 to 700 ° C. to form the undercoat film 14. The undercoat film 14 is formed by reacting zinc oxide with SiO ₂ in the glass substrate 12 when the dispersion liquid described later is baked at a high temperature of 640 ° C. or higher to form the ultraviolet blocking film 16. To prevent vitrification, and when Na is contained in the glass substrate 12, the promotion of vitrification of zinc oxide due to this Na component is suppressed, thereby forming the ultraviolet blocking film 16. This is to widen the allowable range of firing temperature and firing time. As the glass substrate 12 here, the same one as that used in the method of manufacturing the first ultraviolet blocking glass 10 described above can be used. As a coating method of the organopolysiloxane for forming the undercoat film, various coating methods such as a spin coating method, a dipping method and a spraying method can be adopted. The organopolysiloxane for forming the undercoat film is not particularly limited in terms of production method, molecular weight, molecular structure, etc., and organic components are decomposed and dissociated after heating to finally form an amorphous SiO ₂ film. Therefore, it includes those obtained by the sol-gel method using a hydrolyzed solution of alkyl silicate.

Here, the coating amount of the organopolysiloxane for forming the undercoat film is 0.05 μm as the film thickness when dried.
The reason why the thickness is set to 0.6 μm or less is that the undercoat film 14 obtained is too thin if the film thickness is less than 0.05 μm, and the glass substrate 12 coated with the dispersion liquid described below has a high temperature of 640 ° C. or higher. When the ultraviolet blocking film 16 is formed by baking with, the zinc oxide easily reacts with SiO ₂ in the glass substrate 12 to be vitrified, and when the glass substrate 12 contains Na, the Na component is It diffuses even to the ultraviolet blocking film, so that promotion of vitrification of zinc oxide cannot be suppressed. On the other hand, if the coating amount is more than 0.6 μm, the undercoat film may be cracked during firing.

The reason why the baking temperature of the glass substrate 12 coated with the organopolysiloxane for forming the undercoat film is 120 ° C. to 700 ° C. is that the baking temperature is 12 ° C.
If the temperature is lower than 0 ° C., the hardness of the obtained undercoat film 14 is insufficient, and there is a possibility that the undercoat film 14 is redissolved when the dispersion liquid for forming the ultraviolet blocking film is applied in a later step. On the other hand, if the firing temperature exceeds 700 ° C., it is difficult to maintain the original shape of the glass substrate 12 and the glass substrate 12 may be deformed, which is not preferable.

Further, as described above, the undercoat film 1
Since SiO ₂ forming 4 may be crystalline or amorphous, as a method of forming the undercoat film 14, a sputtering method, a vapor deposition method or the like can be adopted. From the viewpoint of productivity and cost, a method of applying and baking an organopolysiloxane is preferable.

Next, the above-mentioned first ultraviolet blocking glass 10
The coating solution is applied onto the undercoat film 14 so as to have a dry film thickness of 0.2 to 1.5 μm in the same manner as that used in the method for producing the above. In the same manner as the manufacturing method, the glass substrate 12
The ultraviolet blocking film 16 is formed by baking at 0 to 700 ° C.
Here, the coating amount of the dispersion liquid is made to be 0.2 μm or more and 1.5 μm or less in the dry film thickness when the thickness is less than 0.2 μm and the method for producing the first ultraviolet blocking glass 10 described above. It is not preferable for the same reason. On the other hand, 1.5 μm
This is because if the amount of coating exceeds the range, cracks may occur during the firing process.

The firing temperature of the glass substrate 12 is set to 520.
The reason why the temperature is set to not lower than 700 ° C. and not higher than 520 ° C. is not preferable for the same reason as the method for manufacturing the first ultraviolet blocking glass 10 described above. On the other hand, when the temperature exceeds 700 ° C., the softening temperature of the glass is exceeded, and it becomes difficult for the glass substrate 12 to keep its original shape, and zinc oxide dissolves in SiO ₂ in the organopolysiloxane serving as a binder.
This is because the rate of vitrification may be increased and an ultraviolet blocking film having a sufficient ultraviolet absorbing power may not be obtained.

The firing time of the glass substrate 12 is 10 to 60 in Japanese Patent Application No. 4-294674.
Although the minute is set in a preferable range, it can be set to 10 minutes or more and 120 minutes or less because the undercoat film 14 is formed in the present invention. Here, the firing time is 10 minutes or more 1
20 minutes or less is the above-mentioned first ultraviolet blocking glass 1
This is for the same reason as the method of manufacturing 0. Regarding the cooling of the fired glass, either slow cooling or rapid cooling may be used,
If it is slowly cooled, it becomes a normal plate glass, while if it is rapidly cooled, it becomes a tempered glass. It is also possible to mold in a softened state, and these steps do not affect the performance of the undercoat film 14 and the ultraviolet blocking film 16. According to the third ultraviolet blocking glass 30 thus obtained, the glass substrate 1
2 is formed between the ultraviolet blocking film 16 and the ultraviolet blocking film 16, zinc oxide is prevented from reacting with SiO ₂ in the glass substrate 12 and vitrifying when the ultraviolet blocking film 16 is formed. Further, when Na is contained in the glass substrate 12, the promotion of vitrification of zinc oxide due to the Na component is suppressed, so that the firing temperature and the firing time when forming the ultraviolet blocking film 16 are suppressed. The allowable range of is expanded.

Next, the ultraviolet blocking glass according to claim 7 of the present invention will be described. FIG. 5 is a schematic configuration diagram showing an example of the ultraviolet blocking glass (hereinafter, abbreviated as fourth ultraviolet blocking glass) according to claim 7, and reference numeral 40 in FIG.
Is a fourth ultraviolet blocking glass 40. This fourth ultraviolet blocking glass differs from the first ultraviolet blocking glass 10 shown in FIG. 1 in that the thickness of the ultraviolet blocking film 16 is 0.2 to 1.
The protective film 18 having a thickness of 5 μm and made of amorphous SiO ₂ and having a thickness of 0.1 to 0.6 μm is the ultraviolet blocking film 1.
6 is a point formed on the upper surface.

In order to manufacture such a fourth UV blocking glass 40, first, the dispersion is dried to a film thickness of 0.2-.
It is coated on the glass substrate 12 to have a thickness of 1.5 μm, and the glass substrate 12 is 120 to 700 ° C., preferably 5
The ultraviolet light shielding film 16 is formed in the same manner as in the method for producing the first ultraviolet light shielding glass 10 described above except that it is baked at 20 to 700 ° C.
To form. Here, the coating amount of the dispersion liquid was set to 0.
The reason why the thickness is set to 2 μm or more and 1.5 μm or less is for the same reason as the method for manufacturing the third ultraviolet blocking glass 10 described above. Further, in the method for producing an ultraviolet blocking glass described in Japanese Patent Application No. 4-294674, the firing temperature range of the glass substrate is 580 to 700 ° C., but in the present invention, the protective film 18 is formed in the subsequent step. Since the high temperature baking is performed at this time, the ultraviolet blocking film 16 before the formation of the protective film 18 has only to be cured to such an extent that the organopolysiloxane solution used for forming the protective film 18 can be applied, and therefore 120 ° C. The firing temperature may be about the same.
However, if the baking temperature is lower than 120 ° C., the curing of the organopolysiloxane in the dispersion liquid that forms the ultraviolet blocking film is not sufficient, and there is a risk that the organopolysiloxane solution for forming the protective film may be redissolved by the solvent. Because there is. On the other hand, if the firing temperature exceeds 700 ° C., the same inconvenience as in the method of manufacturing the third ultraviolet blocking glass 10 may occur.

In particular, the firing temperature is 520 ° C. or higher and 700
It is preferable that the temperature is not higher than 0 ° C. If the hardness of the ultraviolet blocking film 16 is sufficiently high in advance, when the organopolysiloxane solution for forming the protective film is applied on the ultraviolet blocking film 16 in a later step and baked, the protective film is formed. This is because the baking temperature and baking time of the glass substrate 12 coated with the organopolysiloxane solution for forming can be shortened. Furthermore, by preliminarily hardening the ultraviolet blocking film 16 as the base, the abrasion resistance of the resulting protective film 18 becomes higher. However, even if the baking temperature of the ultraviolet blocking film is less than 520 ° C., the protective film having high abrasion resistance can be obtained depending on the baking temperature and the baking time of the glass substrate 12, and thus the glass substrate 12 coated with the dispersion liquid can be used. The firing temperature is 1
A temperature of 20 ° C. or higher and 700 ° C. or lower can be suitable. The firing time of the glass substrate 12 coated with the dispersion is preferably 10 minutes or more and 120 minutes or less depending on the firing temperature. If the baking time is less than 10 minutes, the organopolysiloxane is not sufficiently mineralized, that is, the organopolysiloxane is not sufficiently cured, and a film having good scratch resistance and abrasion resistance cannot be obtained. Even if it exceeds 120 minutes, it does not contribute to the improvement of the film strength, but on the contrary, vitrification of zinc oxide is promoted, and the ultraviolet absorption performance of the formed film may be deteriorated.

Then, a protective film 18 made of amorphous SiO 2 and having a thickness of 0.1 to 0.6 μm is formed on the ultraviolet blocking film 16.
To form. As a method of forming such a protective film 18, sputtering, vapor deposition, a sol-gel method of silicon alkoxide, a silica sol solution, or a method of coating and baking an organopolysiloxane solution for forming a protective film can be considered. In order to form the protective film 18 having the above-described thickness, it is preferable to apply the organopolysiloxane solution on the ultraviolet blocking film 16 and then bake the glass substrate 12. The reason is that it takes a long time to form the protective film 18 having a film thickness of 0.1 μm or more by other methods,
This is because it cannot be formed by a single application, and many layers must be applied.

The organopolysiloxane used in the organopolysiloxane solution for forming the protective film may be the same as that used for forming the ultraviolet blocking film 16, and may have a different molecular weight and molecular structure. It may be one. The organopolysiloxane used herein preferably has a molecular weight of 500 to 150,000. Polysiloxane having a molecular weight of 500 to 150,000 is preferable because when the molecular weight is less than 500, it is difficult to obtain a protective film having a film thickness of 0.1 μm or more. This is because when siloxane heat-polymerizes, cracks may occur due to shrinkage of the film. On the other hand, when the molecular weight exceeds 150,000, it is necessary to bond a large amount of organic groups in order to maintain a stable solution state,
In that case, it is difficult to obtain a hard protective film, and cracks may occur in the film when a large amount of organic groups are decomposed in the baking step.

Usually, in the organopolysiloxane, the terminal group of the siloxane bond is a methyl group or a phenyl group, but in the present invention, it is preferable to use a methyl group. When the terminal group of the siloxane bond is a phenyl group, it is considered that the organopolysiloxane is not easily thermally decomposed and is not completely mineralized. In that case, the hardness of the protective film may be insufficient. Further, since the molecular weight is large, there is a possibility that problems such as large film shrinkage and generation of cracks may occur when thermally decomposed. Moreover, the terminal groups of the siloxane bond are more
Those partially having hydroxyl groups are preferable. Making part of the terminal groups hydroxyl groups facilitates condensation polymerization of the film during heating,
This is because the protective film can be hardened. However, when all the terminals of the polysiloxane are hydroxyl groups, the polysiloxane is easily polymerized and the stability as a solution cannot be maintained.

Generally, the molecular structure of polysiloxane includes chain-like, cyclic, ladder-like, cage-like, and three-dimensional stitch-like ones, but a chain-like or cyclic structure cannot provide a hard protective film. Therefore, in the present invention, ladder-shaped, basket-shaped, and three-dimensional stitch-shaped ones are preferable. The concentration of such an organopolysiloxane is appropriately adjusted according to the coating method and the coating conditions to obtain an organopolysiloxane solution for forming a protective film. As a coating method of the organopolysiloxane solution for forming the protective film on the ultraviolet blocking film 14, various coating methods such as a spin coating method, a dip coating method and a spraying method can be adopted.

The coating amount of the organopolysiloxane solution for forming the protective film is such that the dry film thickness is 0.1 μm or more and 0.6 or less. This is because if the obtained film thickness is less than 0.1 μm, sufficient acid resistance cannot be imparted and it is insufficient as a protective film. On the other hand, if the coating amount is more than 0.6, cracks may occur when firing at 520 ° C. or higher in the subsequent firing step.

The firing temperature of the glass substrate 12 coated with the protective film-forming organopolysiloxane solution on the ultraviolet blocking film 16 is preferably 520 ° C. or higher and 700 ° C. or lower. When the firing temperature is lower than 520 ° C., the organopolysiloxane used for forming the ultraviolet blocking film 16 and the protective film 18 is not sufficiently thermally decomposed to form inorganic SiO ₂ , and the ultraviolet blocking film 16 and the protective film having high hardness are obtained. Since 18 is not obtained, it is not suitable for glass that requires hard abrasion resistance and abrasion resistance, such as automobiles and architectural window glass. On the other hand, when the temperature exceeds 700 ° C., the softening temperature of the glass is exceeded, and it becomes difficult for the glass substrate 12 to keep its original shape, and the zinc oxide of the lower ultraviolet blocking film 16 is SiO ₂ in the organopolysiloxane serving as the binder. This is because there is a possibility that the ultraviolet blocking film 16 having a sufficient ultraviolet absorbing power may not be obtained because the ultraviolet blocking film 16 dissolves in the glass and accelerates vitrification.

Further, a glass substrate 1 in which an organopolysiloxane solution for forming a protective film is coated on the ultraviolet blocking film 16
The firing time of 2 is 10 minutes or more and 120 or less. Because, if it is less than 10 minutes, the ultraviolet blocking film 16 and the protective film 18 are insufficiently cured, and the ultraviolet blocking film and the protective film having good scratch resistance and abrasion resistance cannot be obtained.
Even if heated for more than 20 minutes, it does not contribute to the improvement of the hardness of the ultraviolet blocking film 16 and the protective film 18, and conversely vitrification of zinc oxide in the organopolysiloxane used for forming the ultraviolet blocking film 16. This is because there is a risk that the UV blocking performance of the formed UV blocking film 16 is deteriorated.

Regarding the cooling of the baked glass, slow cooling,
Any of rapid cooling may be used, and if gradually cooled, it becomes a normal plate glass, while if rapidly cooled, it becomes a tempered glass. It is also possible to mold in a softened state, and these steps do not affect the performance of the ultraviolet blocking film 16 and the protective film 18.

According to the fourth ultraviolet blocking glass 40 thus obtained, since the protective film 18 is formed on the ultraviolet blocking film 16, the fourth ultraviolet blocking glass 40 is protected from acid rain and exhaust gas. The zinc oxide in the ultraviolet blocking film 16 can be prevented from dissolving even when it comes into contact with a dissolved liquid, so that the acid resistance is improved, and the surface hardness is sufficiently high, and the scratch resistance, It has excellent wear resistance.

Next, the ultraviolet blocking glass according to claim 9 of the present invention will be described. FIG. 6 is a schematic configuration diagram showing an example of the ultraviolet blocking glass according to claim 9 (hereinafter abbreviated as fifth ultraviolet blocking glass), and reference numeral 50 in FIG.
Is a fifth ultraviolet blocking glass. The fifth ultraviolet blocking glass 50 differs from the fourth ultraviolet blocking glass 40 shown in FIG. 5 in that it is made of SiO2 between the glass substrate 12 and the ultraviolet blocking film 16 and has a thickness of 0.05 to 0. .6 μm
That is, the undercoat film 14 is formed. In order to manufacture such a fifth UV blocking glass 50, the undercoat film 14 is formed in the same manner as in the method for manufacturing the third UV blocking glass 30 described above, and then the fourth UV blocking glass 40 described above is formed. After forming the ultraviolet blocking film 16 in the same manner as in the manufacturing method, the protective film 18 may be formed.

According to the fifth ultraviolet blocking glass 50 thus obtained, the glass substrate 12 and the ultraviolet blocking film 16 are provided.
Since the undercoat film 14 is formed between and, the zinc oxide is prevented from reacting with SiO ₂ in the glass substrate 12 to vitrify when the ultraviolet blocking film 16 is formed. When Na is included in 12, the promotion of vitrification of zinc oxide due to the Na component is suppressed, so that the allowable range of the baking temperature and the baking time for forming the ultraviolet blocking film 16 should be widened. Is possible. Further, since the protective film 18 is formed on the glass substrate 12 and the ultraviolet blocking film 16, even if the fourth ultraviolet blocking glass 40 comes into contact with acid rain, exhaust gas or the like, zinc oxide in the ultraviolet blocking film 16 Can be prevented from being dissolved, so that the acid resistance is improved, the surface hardness is sufficiently high, and the abrasion resistance and abrasion resistance are excellent.

[0048]

EXAMPLES The present invention will be described in more detail with reference to Examples. (Examples 1 to 8) Methyltriethroxysilane 100 parts by weight, isopropyl alcohol 100 parts by weight, pure water 30
Part by weight 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 allowed to react for 2 hours while maintaining at 150 ° C. in an oil bath to obtain a viscous transparent liquid. . Next, this liquid was distilled under reduced pressure of 5 to 20 mmHg to obtain 37 parts by weight of a white solid (organopolysiloxane). 30 parts by weight of the obtained white solid,
70 parts by weight of zinc oxide fine powder (Sumitomo Cement Co., Ltd., trade name [ZnO-100]) having a particle size of 0.1 μm or less, 100 parts by weight of butyl acetate, 100 parts by weight of isopropanol, and 50 parts by weight of toluene are mixed and sanded. A white liquid was obtained by dispersing with a grinder for 3 hours. This white liquid was used as a dispersion liquid. Next, ordinary soda lime glass was prepared as a glass substrate. Then, the number of revolutions of the dispersion liquid was changed by a spin coater and applied on one surface of the ordinary soda lime glass so that the film thickness after drying was 0.2 μm to 1.0 μm. In addition, the above-mentioned dispersion liquid is applied to a film thickness of 0.1 μm to 1.2.
It was applied to both sides of the ordinary soda lime glass so as to have a thickness of μm. Then, these ordinary soda lime glass is heated at 520 to 640 ° C.
The glass was placed in an electric furnace set between the two, and after the glass temperature reached the set temperature, the glass was baked for 10 to 120 minutes to form an ultraviolet blocking film, and an ultraviolet blocking glass was obtained. Then, the obtained ultraviolet blocking glass was evaluated for scratch resistance, abrasion resistance, and moldability. The results are shown in Table 1 below. The evaluation of the scratch resistance and the wear resistance herein was carried out by using the obtained ultraviolet blocking glass with a Taber type wear resistance tester (wear wheels CS-10F, 5
It was carried out by measuring the change (%) in the haze value before and after abrasion under a load of 00 g and 1000 rotations. The moldability was evaluated by placing the obtained ultraviolet blocking glass in an electric furnace set at 730 ° C., holding it for 10 minutes, and measuring the amount of warpage (mm).

(Comparative Examples 1 to 4) The same ordinary soda lime glass used in the above examples was prepared. Next, the number of revolutions of the dispersion liquid obtained in the above example was changed by a spin coater, and the dispersion liquid was applied to one surface of the ordinary soda lime glass so as to have a film thickness of less than 0.2 μm or more than 1.0 μm. Also,
The dispersion was applied on both sides of the ordinary soda lime glass so that the film thickness was less than 0.1 μm or more than 1.2 μm. Then, these ordinary soda lime glass was placed in an electric furnace set at 520 to 640 ° C., and after the glass temperature reached the set temperature, it was fired for 10 to 120 minutes to form an ultraviolet blocking film to obtain an ultraviolet blocking glass. . Then, the obtained ultraviolet blocking glass was evaluated for scratch resistance, abrasion resistance, and moldability in the same manner as in the above-described examples. The results are shown in Table 2 below.

[0050]

[Table 1]

[0051]

[Table 2]

In Tables 1 and 2 above, ◯ indicates that the abrasion resistance, abrasion resistance and moldability were good, and Δ indicates the abrasion resistance,
It shows that the wear resistance is good, but the moldability is poor.

As is clear from the results shown in Tables 1 and 2, the ultraviolet blocking glasses of Comparative Examples 1 and 2 have a haze change of 4% or less and have sufficient scratch resistance as a window glass for automobiles. It has abrasion resistance, but the warp amount is 2.0 to 5.
It may be as large as 0 mm and moldability may be insufficient. I understand. In contrast, the ultraviolet blocking films obtained in Examples 1 to 8 had a haze change of 4% or less and had not only sufficient scratch resistance and abrasion resistance as a window glass for automobiles, but also the amount of warpage. It can be seen that the moldability is excellent because it is 1.0 mm or less.

Example 9 A dispersion was prepared in the same manner as in Examples 1 to 8 above. Further, the white solid (organopolysiloxane) obtained in Examples 1 to 8 was dissolved in a 1: 1 mixed solution of butyl acetate and isopropanol,
% Solution. This solution was used as an undercoat liquid. Then, cleaned soda-lime glass was prepared as a glass substrate. Then, the undercoat solution was applied onto the soda-lime glass by spin coating so that the film thickness after drying was 0.2 μm, and then baked at 350 ° C. to form an undercoat film. Then, the dispersion is applied on the undercoat film by spin coating so that the film thickness after drying is 0.8 μm, and then baked at 650 ° C. for 30 minutes to form an ultraviolet blocking film, and an ultraviolet blocking film is formed. I got a glass. Then, the spectral transmittance (%) of the obtained ultraviolet blocking glass was examined. The result is shown in FIG. 7. In FIG. 7, the curve shows the relationship between the wavelength (nm) of the ultraviolet rays applied to the ultraviolet blocking glass of Example 9 and its transmittance (%).

(Comparative Example 5) The dispersion liquid used in the above-mentioned Example 9 was directly coated on soda-lime glass so as to have a film thickness of 0.8 μm when dried, and was baked under the same baking conditions as in the above-mentioned Example 9. Thus, an ultraviolet blocking film was formed to obtain an ultraviolet blocking glass.
And the spectral transmittance (%) of the obtained UV blocking glass
I checked. The result is shown in FIG. 7. In FIG. 7, the curve shows the wavelength (n of the light irradiated onto the ultraviolet blocking glass of Comparative Example 5).
m) and its transmittance (%).

As is clear from the results shown in FIG. 7, the transmittance of the UV blocking glass of Comparative Example 5 having no undercoat film is about 13% of UV of 300 to 380 nm, whereas It can be seen that the ultraviolet blocking glass of Example 9 having the film hardly transmits ultraviolet rays of 380 nm or shorter. This is because in the ultraviolet blocking glass of Comparative Example 5, zinc oxide was vitrified and the ultraviolet absorbing power was lowered in baking at 650 ° C. for 30 minutes, whereas the ultraviolet blocking glass of Example 9 was oxidized. It is shown that vitrification of zinc does not occur and the ultraviolet absorption is excellent.

(Example 10) An ultraviolet blocking glass was obtained in the same manner as in Example 9 except that the firing temperature for forming the ultraviolet blocking film was set in the range of 520 to 700 ° C. Then, the abrasion resistance and the ultraviolet transmittance of the obtained ultraviolet blocking glass were examined. The result is shown in FIG. For the evaluation of wear resistance, the obtained ultraviolet blocking glass was subjected to Taber-type wear resistance tester (wear wheel CS-10F, 500 g load, 100
Change of haze value before and after abrasion [0H]
(%)]. The haze value of the glass before the abrasion test was 0.2%. Further, the ultraviolet transmittance is shown by the transmittance (%) when irradiated with 350 nm ultraviolet light. In FIG. 8, the curve shows the relationship between the baking temperature (° C.) of the ultraviolet blocking glass and the change (%) of the haze value, and the curve shows the baking temperature (° C.) and the ultraviolet transmittance (%) of the ultraviolet blocking glass of Example 10. ) With the relationship.

(Comparative Example 6) An ultraviolet blocking glass was obtained in the same manner as in Comparative Example 5 except that the firing temperature for forming the ultraviolet blocking film was set in the range of 520 to 700 ° C. Then, the abrasion resistance and the ultraviolet transmittance of the obtained ultraviolet blocking glass were examined in the same manner as in Example 10 above. The result is shown in FIG. In FIG. 8, the curve shows the relationship between the baking temperature (° C.) and the ultraviolet transmittance (%) of the ultraviolet blocking glass of Comparative Example 6.
As is clear from the results shown in FIG. 8, the firing temperature range satisfying the performance that is practically sufficient for the ultraviolet blocking glass, that is, the change in haze value of 4% or less and the ultraviolet transmittance of 10% or less is the firing time. In the case of 30 minutes, the ultraviolet blocking glass of Comparative Example 6 having no undercoat film has a range of AB in FIG. 8, that is, a range of 575 to 620 ° C. On the other hand, in the ultraviolet blocking glass of Example 10,
AC range, i.e. 575-685 ° C range,
It can be seen that the firing temperature range is about 55 ° C. wider than that of Comparative Example 6.

(Examples 11 to 15) Dispersions were prepared in the same manner as in Examples 1 to 8 above. Further, the white solid (organopolysiloxane) obtained in Examples 1 to 8 was dissolved in isopropanol to prepare a liquid having a nonvolatile content of 8%. This solution was used as a protective film forming solution. Then, the above-mentioned dispersion liquid was applied to ordinary soda lime glass by a spin coating method so that the film thickness when dried was 0.8 μm. Then, the ordinary soda lime glass coated with this dispersion was put into an electric furnace set at 120 to 700 ° C., and baked for 40 minutes after the glass temperature reached the set temperature to form an ultraviolet blocking film. Next, the protective film-forming liquid was applied on the ultraviolet blocking film by a spin coating method so that the film thickness when dried was 0.1 to 0.6 μm, and then the electrical resistance was set between 520 and 700 ° C. The glass was placed in a furnace and baked for 40 minutes after the glass temperature reached the set temperature to form a protective film, thus obtaining an ultraviolet blocking glass. Then, the obtained ultraviolet blocking glass was evaluated for abrasion resistance and acid resistance. The results are shown in Table 3 below. The evaluation of the abrasion resistance here was performed in the same manner as in Examples 1 to 8 above. The haze value of the UV blocking glass before the abrasion test is 0.2
%Met. The acid resistance was evaluated by using a sulfuric acid aqueous solution (pH 1.
0) was added dropwise, and the mixture was evaporated to dryness at 70 ° C., and then the transmittance at 360 nm at the dropped position was measured. The transmittance of the ultraviolet blocking glass before the acid resistance test was 3.5%.

(Comparative Example 7) Except that a protective film is not formed,
An ultraviolet blocking glass was obtained in the same manner as in Examples 11 to 15 above. Here, the firing temperature for forming the ultraviolet blocking film was 580 ° C., and the firing time was 40 minutes. Then, the abrasion resistance and the acid resistance of the obtained ultraviolet blocking glass were evaluated in the same manner as in Examples 11 to 15 above. The results are shown in Table 3 below.

(Comparative Examples 8 to 9) The same procedures as in Examples 11 to 15 were repeated, except that the thickness of the protective film forming liquid when dried by spin coating was 0.08 μm or 0.7 μm. An ultraviolet blocking glass was obtained. Then, the abrasion resistance and the acid resistance of the obtained ultraviolet blocking glass were evaluated in the same manner as in Examples 11 to 15 above. The results are shown in Table 3 below.
Shown in.

[0062]

[Table 3]

In Table 3, ∘ indicates that the wear resistance and acid resistance were good, and x indicates that the wear resistance was good but the acid resistance was poor.

As is clear from the results shown in Table 3 above,
The ultraviolet blocking glass of Comparative Example 7 had sufficient wear resistance, but had insufficient acid resistance because it did not have a protective film. The protective film of the ultraviolet blocking glass of Comparative Example 8 was too thin and the acid resistance was insufficient, and the protective film of the ultraviolet blocking glass of Comparative Example 9 was too thick, and microcracks were generated in the film, resulting in acid resistance. It turns out that it is also decreasing. In comparison with this, Example 1
It can be seen that the ultraviolet blocking glasses 1 to 15 have excellent wear resistance and acid resistance.

[0065]

As described above, in the ultraviolet blocking glass according to the first aspect of the invention, since the thickness of the ultraviolet blocking film and the firing temperature are specified within the above ranges, abnormalities are caused during heating during molding. Deformation, glass breakage, defective dimensions,
It is possible to prevent defects such as surface distortion from occurring, and it is excellent in scratch resistance and abrasion resistance, and also in moldability. Therefore, by using this ultraviolet blocking glass, defective products are less likely to occur during molding, and the yield is improved. Further, in the ultraviolet blocking glass according to claim 3, the film thickness and the baking temperature of the ultraviolet blocking film are specified within the above range, and the ultraviolet blocking glass is formed on both surfaces of the glass substrate. It has the same effect as the ultraviolet blocking glass described in 1.

Further, in the ultraviolet blocking glass according to the fifth aspect, since the undercoat film is formed between the glass substrate and the ultraviolet blocking film, when the ultraviolet blocking film is formed, zinc oxide is contained in the glass substrate. It is prevented from reacting with SiO ₂ in the glass and vitrifying, and when Na is contained in the glass substrate, promotion of vitrification of zinc oxide due to this Na component is suppressed. The firing temperature and the firing time for forming the ultraviolet blocking film can be widely set without impairing the scratch resistance and abrasion resistance. Therefore, there is an advantage that the tolerance for the variation of the manufacturing conditions of the ultraviolet blocking glass becomes large, which is convenient in production and easy to manufacture. Further, in the ultraviolet blocking glass according to claim 7, since the protective film is formed on the ultraviolet blocking film, even if the ultraviolet blocking glass comes into contact with acid rain or a liquid in which exhaust gas is dissolved, Since it is possible to prevent zinc oxide in the ultraviolet blocking film 16 from coming into contact with an acid to be dissolved, the acid resistance is improved, the surface hardness is sufficiently high, and the scratch resistance and the abrasion resistance are excellent. .

Further, in the ultraviolet blocking glass according to claim 9, since the undercoat film is formed between the glass substrate and the ultraviolet blocking film, when the ultraviolet blocking film is formed, zinc oxide is contained in the glass. It is prevented from vitrifying by reacting with SiO _{2 in the} substrate, and Na in the glass substrate is prevented.
Since the promotion of vitrification of zinc oxide due to this Na component is suppressed when the content of Na is included, the allowable range of the baking temperature and the baking time when forming the ultraviolet blocking film can be expanded. Further, since the protective film is formed on the glass substrate and the ultraviolet blocking film, zinc oxide in the ultraviolet blocking film is dissolved even when the ultraviolet blocking glass comes into contact with acid rain or a liquid in which exhaust gas is dissolved. Therefore, the acid resistance is improved, the surface hardness is sufficiently high, and the abrasion resistance and abrasion resistance are excellent.

Further, according to the method for producing an ultraviolet blocking glass of the present invention, the permissible range of the firing temperature and the firing time is wide, at least one of the moldability and the acid resistance is excellent, and the abrasion resistance and the abrasion resistance are excellent. It is possible to easily and economically manufacture an ultraviolet blocking glass having excellent abrasion resistance. This UV blocking glass has a large UV blocking effect, has the same wear resistance as ordinary flat glass, and the one with a protective film has acid resistance, so it is an interior material for vehicles and buildings. Prevents fading and deterioration of furniture. Therefore, by using such an ultraviolet blocking glass for a window glass for an automobile or a building, the interior of the automobile can be made of materials, color sheet materials, interior materials, furniture, etc. that could not be used until now because of fear of fading or deterioration due to ultraviolet rays. Can be used in the building. In addition, automobile window glass is extremely effective in preventing the sunburn of its occupants.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing an example of an ultraviolet blocking glass according to claim 1.

FIG. 2 is a graph showing the relationship between firing temperature (° C.) and firing time (minutes) and haze change [ΔH (%)].

FIG. 3 is a schematic configuration diagram showing an example of the ultraviolet blocking glass according to claim 3.

FIG. 4 is a schematic configuration diagram showing an example of the ultraviolet blocking glass according to claim 5.

FIG. 5 is a schematic configuration diagram showing an example of the ultraviolet blocking glass according to claim 7.

FIG. 6 is a schematic configuration diagram showing an example of the ultraviolet blocking glass according to claim 9.

7 is a graph showing the spectral transmittances of the ultraviolet blocking glass obtained in Example 9 and the ultraviolet blocking glass obtained in Comparative Example 5. FIG.

FIG. 8 is a graph showing the abrasion resistance and the ultraviolet transmittance depending on the firing temperature for the ultraviolet blocking glass obtained in Example 10 and the ultraviolet blocking glass obtained in Comparative Example 6.

[Explanation of symbols]

10 ... First UV blocking glass, 12 ... Glass substrate, 1
4 ... Undercoat film, 16 ... UV blocking film, 18 ...
-Protective film, 20 ... second UV blocking glass, 30 ... third UV blocking glass, 40 ... fourth UV blocking glass, 5
0 ... Fifth UV blocking glass.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Tojima 1 Toyota-cho, Toyota City, Aichi Prefecture, Toyota Motor Co., Ltd. (72) Inventor Yasushi Yamazawa 1-cho, Toyota City, Aichi Prefecture, Toyota Motor Co., Ltd. ( 72) Inventor Takashi Ito 1 Toyota Town, Toyota City, Aichi Prefecture, Toyota Motor Co., Ltd. (72) Inventor, Ai Kobayashi, 1 Toyota Town, Toyota City, Aichi Prefecture, Toyota Motor Co., Ltd.

Claims (10)

[Claims] 1. A fine powder of zinc oxide having a particle size of 0.1 μm or less and amorphous SiO ₂ , wherein SiO ₂ /ZnO=0.25.
~ 0.67 (weight ratio) and the thickness is 0.2
An ultraviolet blocking glass having an ultraviolet blocking film having a thickness of about 1.0 μm formed on one surface of a glass substrate. 2. Zinc oxide fine powder having a particle size of 0.1 μm or less is added to an organopolysiloxane solution to obtain SiO ₂ / ZnO =
0.25 to 0.67 (weight ratio) are mixed to obtain a dispersion liquid obtained by dispersing the zinc oxide fine powder, and a dry film thickness of 0.2 to 1.0 μm is obtained. To one side of the glass substrate, and then the glass substrate 52
The method for producing an ultraviolet blocking glass according to claim 1, wherein the ultraviolet blocking film is formed by baking at 0 to 700 ° C. 3. A zinc oxide fine powder having a particle size of 0.1 μm or less and amorphous SiO ₂ , wherein SiO ₂ /ZnO=0.25.
To 0.67 (weight ratio) and the thickness is 0.1
An ultraviolet blocking glass having an ultraviolet blocking film having a thickness of 1.2 μm formed on both surfaces of a glass substrate. 4. Zinc oxide fine powder having a particle size of 0.1 μm or less is added to an organopolysiloxane solution to obtain SiO ₂ / ZnO =
0.25 to 0.67 (weight ratio) are mixed to obtain a dispersion liquid obtained by dispersing the zinc oxide fine powder, and a dry film thickness of 0.1 to 1.2 μm. After coating on both sides of the glass substrate,
The method for producing an ultraviolet blocking glass according to claim 3, wherein the ultraviolet blocking film is formed by baking at 0 to 700 ° C. 5. Made of SiO ₂ and having a thickness of 0.05 to
An undercoat film having a thickness of 0.6 μm is formed on a glass substrate, and further comprises zinc oxide fine powder having a particle diameter of 0.1 μm or less and amorphous SiO ₂ , and SiO ₂ /ZnO=0.25 to
The ratio is 0.67 (weight ratio) and the thickness is 0.2 to
An ultraviolet blocking glass having an ultraviolet blocking film of 1.5 μm formed on the undercoat film. 6. An undercoat film is formed by coating organopolysiloxane on a glass substrate so that the film thickness when dried is 0.05 to 0.6 μm, and baking the glass substrate at 120 to 700 ° C. Then, a zinc oxide fine powder having a particle size of 0.1 μm or less is added to an organopolysiloxane solution to form S.
iO ₂ /ZnO=0.25 to 0.67 (weight ratio) is mixed to obtain a dispersion liquid obtained by dispersing the zinc oxide fine powder in a dry film thickness of 0.2 to 1. The ultraviolet blocking glass according to claim 5, wherein the ultraviolet blocking film is formed by coating the glass substrate at a thickness of 5 μm on the undercoat film and then baking the glass substrate at 520 to 700 ° C. Production method. 7. Zinc oxide fine powder having a particle size of 0.1 μm or less and amorphous SiO ₂ , wherein SiO ₂ /ZnO=0.25.
~ 0.67 (weight ratio) and the thickness is 0.2
An ultraviolet blocking film having a thickness of up to 1.5 μm is formed on a glass substrate, is made of amorphous SiO ₂ , and has a thickness of 0.1.
An ultraviolet blocking glass having a protective film of about 0.6 μm formed on the ultraviolet blocking film. 8. Zinc oxide fine powder having a particle size of 0.1 μm or less is added to an organopolysiloxane solution to obtain SiO ₂ / ZnO =
0.25 to 0.67 (weight ratio) are mixed to obtain a dispersion liquid obtained by dispersing the zinc oxide fine powder to a dry film thickness of 0.2 to 1.5 μm. After coating on a glass substrate so that
The composition is baked at 0 ° C. to form an ultraviolet blocking film, and then organopolysiloxane is coated on the ultraviolet blocking film so that the film thickness when dried is 0.1 to 0.6 μm. The method for producing an ultraviolet blocking glass according to claim 7, wherein the protective film is formed by baking at ~ 700 ° C. 9. Made of SiO2 and having a thickness of 0.05 to
An undercoat film having a thickness of 0.6 μm is formed on a glass substrate, and further comprises zinc oxide fine powder having a particle diameter of 0.1 μm or less and amorphous SiO ₂ , and SiO ₂ /ZnO=0.25 to
The ratio is 0.67 (weight ratio) and the thickness is 0.2 to
An ultraviolet blocking film having a thickness of 1.5 μm is formed on the undercoat film, and a protective film made of amorphous SiO ₂ and having a thickness of 0.1 to 0.6 μm is formed on the ultraviolet blocking film. UV blocking glass. 10. An undercoat film is formed by coating organopolysiloxane on a glass substrate so that the film thickness when dried is 0.05 to 0.6 μm, and baking the glass substrate at 120 to 700 ° C. Formed and then has a particle size of 0.1 μm
A dispersion liquid obtained by mixing the following zinc oxide fine powder with an organopolysiloxane solution in a ratio of SiO ₂ /ZnO=0.25 to 0.67 (weight ratio) to disperse the zinc oxide fine powder. Is coated on the undercoat film so as to have a thickness of 0.2 to 1.5 μm when dried,
The glass substrate is baked at 120 to 700 ° C. to form an ultraviolet blocking film, and then organopolysiloxane is coated on the ultraviolet blocking film so that the dry film thickness is 0.1 to 0.6 μm. The method for producing an ultraviolet blocking glass according to claim 9, wherein the glass substrate is baked at 520 to 700 ° C to form a protective film.