JP2016001201A - Method of producing glass having antireflection property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing glass having both an antiglare property and an antireflection property.SOLUTION: The present invention relates to a method of producing glass having an antireflection property, the method including steps of (a) preparing a glass substrate having a surface having an antiglare property, and (b) bringing a process gas including a fluorine compound into contact with the surface of the glass substrate at normal pressure, in the atmosphere, and in a temperature range of 250°C-650°C.

Description

  The present invention relates to a method for producing an antireflective glass.

  For example, high light transmittance may be required in various glass products such as glass for building materials, glass for display panels, optical elements, glass for solar cell panels, show window glass, optical glass, and eyeglass lenses. In such a case, a glass substrate having antireflection properties is used.

  Such an antireflection glass substrate is formed by, for example, coating the surface of the glass substrate with a low refractive index material by an immersion method, or a multilayer film on the surface of the glass substrate by a dry method such as vapor deposition or sputtering. Or the like can be formed.

Special table 2009-529715

  As described above, when manufacturing a glass product that requires high light transmittance, a glass substrate having an antireflection film formed on the surface by various methods is used.

  On the other hand, for example, antiglare properties may be required for the above glass products in order to suppress glare due to reflection. In this case, it is necessary to intentionally roughen the surface of the glass substrate and perform a process of forming irregularities on the order of μm on the surface.

  However, it is extremely difficult to properly form an antireflection film on a glass substrate having such irregularities on the surface. In addition, if the thickness of the formed antireflection film is deviated from a predetermined range or the uniformity of the film thickness is poor, the glass substrate cannot exhibit desired antireflection properties. .

  This invention is made | formed in view of such a problem, and an object of this invention is to provide the manufacturing method of glass which has both anti-glare property and antireflection property.

In the present invention, a method for producing an antireflective glass,
(A) providing a glass substrate having an anti-glare surface;
(B) contacting a treatment gas containing a fluorine compound with the surface of the glass substrate in a temperature range of 250 ° C. to 650 ° C. under normal pressure and atmospheric atmosphere;
The manufacturing method of the glass which has antireflective property characterized by having is provided.

  Here, in the production method according to the present invention, the fluorine compound may contain hydrogen fluoride and / or trifluoroacetic acid.

  In the production method according to the present invention, the concentration of hydrogen fluoride gas in the processing gas may be in the range of 0.1 vol% to 10 vol%.

  In the manufacturing method according to the present invention, the processing gas may further contain nitrogen and / or argon.

  In the manufacturing method according to the present invention, the arithmetic average roughness Ra of the surface of the glass substrate after the step (b) is 10 nm or more, and the maximum height roughness Rz is 0.3 μm or more. May be.

  In the manufacturing method according to the present invention, in the step (b), the glass substrate may be brought into contact with the processing gas in a transported state.

Further, in the manufacturing method according to the present invention, an injector is disposed on the upper part of the glass substrate,
The processing gas may be emitted from the injector toward the glass substrate.

  Further, in the manufacturing method according to the present invention, the injector is not limited to the upper portion of the glass substrate, and may be disposed at the lower portion. The time for the glass substrate to pass under the injector may be between 1 second and 120 seconds.

  In the manufacturing method according to the present invention, the total light transmittance of the glass substrate after the step (b) and the total light transmittance of the glass substrate after the step (a) and before the step (b). The difference ΔTt may be 1% or more.

  In the manufacturing method according to the present invention, the step (a) includes performing at least one selected from the group consisting of blasting, wet processing, and embossing on the glass substrate. May be. A plurality of processes may be combined.

  In the manufacturing method according to the present invention, the glossiness on the surface of the glass substrate after the step (b) may be 70% or less.

  Moreover, in the manufacturing method by this invention, the panel for solar cells or the panel for a display may be sufficient as the said glass.

  In the present invention, a method for producing glass having both antiglare property and antireflection property can be provided.

It is the figure which showed schematically the flow of the manufacturing method of the glass by one Example of this invention. It is the figure which showed the example of 1 structure of the processing apparatus for implementing the etching process of a glass substrate in the state which conveyed the glass substrate.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

In the present invention, a method for producing an antireflective glass,
(A) providing a glass substrate having an anti-glare surface;
(B) contacting a processing gas containing a gaseous fluorine compound with the surface of the glass substrate in a temperature range of 250 ° C. to 650 ° C. under normal pressure and atmospheric atmosphere;
The manufacturing method characterized by having is provided.

  As described above, when manufacturing a glass product that requires high light transmittance, a glass substrate having an antireflection film formed on the surface by various methods is used.

  On the other hand, for example, antiglare properties may be required for the above glass products in order to suppress glare due to reflection. In this case, it is necessary to intentionally roughen the surface of the glass substrate and perform a process of forming irregularities on the surface.

  However, it is extremely difficult to properly form an antireflection film on a glass substrate having such irregularities on the surface. In addition, if the thickness of the formed antireflection film is deviated from a predetermined range or the uniformity of the film thickness is poor, the desired antireflection property cannot be exhibited on the glass substrate.

  On the other hand, the glass manufacturing method according to the present invention exhibits antireflection properties by etching using gas. For this reason, precise refractive index control and film thickness control on the surface of the glass substrate, which are essential in a method of developing antireflection properties such as a conventional lamination method, are not required in the present invention.

  The glass manufacturing method according to the present invention includes the step of (b) bringing a processing gas containing a gaseous fluorine compound into contact with the surface of the glass substrate in a temperature range of 250 ° C. to 650 ° C. under normal pressure and atmospheric atmosphere. It has the characteristics.

  In this step, the surface of the glass substrate having irregularities can be etched, for example, on the order of 1 nm to 200 nm. In addition, according to the inventors of the present application, it has been confirmed that antireflection properties can be expressed with respect to the glass substrate even by such a fine etching process.

  Thus, in the manufacturing method according to the present invention, the glass substrate is made to exhibit antireflection properties by a fine etching process. For this reason, in the manufacturing method according to the present invention, the surface of the glass substrate has a uniform thickness and is substantially perpendicular to the (depth) direction without being affected by the uneven shape formed in advance on the surface of the glass substrate. The unevenness is further formed, and the treatment for imparting antireflection properties to the glass substrate can be appropriately performed. Therefore, in the manufacturing method according to the present invention, it is possible to appropriately carry out the treatment for imparting antireflection properties to a glass substrate having antiglare properties, for example, a glass substrate having irregularities on the order of μm.

  Due to such effects, the present invention can provide a method for producing glass having both antiglare property and antireflection property.

(About the manufacturing method by one Example of this invention)
Next, with reference to drawings, the manufacturing method of the antireflective glass by one Example of this invention is demonstrated in detail.

  In FIG. 1, the flow of the manufacturing method of the glass by one Example of this invention is shown roughly.

As shown in FIG. 1, a method for producing glass according to an embodiment of the present invention includes:
(A) preparing a glass substrate having a surface having antiglare properties (step S110);
(B) a step of bringing a treatment gas containing a fluorine compound into contact with the surface of the glass substrate in a temperature range of 250 ° C. to 650 ° C. under normal pressure and atmospheric atmosphere (step S120);
Have

  Hereinafter, each step will be described.

(Step S110)
First, a glass substrate is prepared.

The kind of glass substrate is not particularly limited. As the glass substrate, for example, a transparent glass substrate made of soda lime glass, soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, quartz glass, borosilicate glass, alkali-free glass, and other various glasses. Can be used.
In particular, the glass substrate preferably contains an alkali element, an alkaline earth element rope, and / or aluminum, such as soda-lime silicate glass or aluminosilicate glass.

  When the glass substrate contains an alkali element, an alkaline earth element, and / or aluminum, the fluorine compound tends to remain on the surface of the glass substrate in the subsequent etching process in step S120.

Such a residual fluorine compound contributes to the improvement of the light transmittance of the glass substrate. That is, the refractive index (n ₁ ) of the residual fluorine compound usually has a refractive index between the refractive index (n ₂ ) of the glass substrate and the refractive index of air (n ₀ ). For this reason, when the glass substrate, the fluorine compound, and the air are arranged in this order, the reflectance as a whole is lowered, and as a result, the light transmittance of the glass substrate is improved.

The glass substrate preferably has a high transmittance in a wavelength region of 350 nm to 800 nm, for example, a transmittance of 80% or more. Further, it is desirable that the glass substrate has sufficient insulation and high chemical and physical durability.
The manufacturing method of the glass substrate is not particularly limited. The glass substrate may be manufactured by a float method, for example.

  Although the thickness of a glass substrate is not specifically limited, For example, the range of 0.1 mm-12 mm may be sufficient.

Note that the glass substrate does not necessarily have to be flat, and the glass substrate may have a curved surface shape or an irregular shape. For example, a surface pattern of a forming roller during glass forming is formed on the surface. Glass called “template” may be used.
Next, a process for imparting antiglare properties (hereinafter referred to as “antiglare process”) is performed on the glass substrate.

  The anti-glare treatment is performed, for example, by roughening the surface of the glass substrate and forming irregularities on the surface.

  Such a process for forming irregularities on the surface may be performed by, for example, a blast process, a wet process, or an embossing process.

  Among these, the blasting process is a general term for a process (for example, a sandblasting process, a water blasting process, a dry ice blasting process, and the like) in which a medium such as alumina collides with the surface of a glass substrate to roughen the surface. Moreover, wet processing means the general term for the process which makes a glass substrate rough by immersing a glass substrate in various solutions. Furthermore, the die pressing process is a general term for a process of transferring a pattern to a glass substrate by pressing a mold having a concavo-convex pattern onto the surface of the glass substrate like a plate glass.

  In the above example, the process of roughening the surface of the glass substrate and imparting anti-glare property by unevenly “removing” the surface of the glass substrate has been described. However, the “anti-glare process” is not limited to such a mode. For example, the surface of the glass substrate may be unevenly formed (eg, silica coating) by coating the surface of the glass substrate with a non-uniform “application” of the same type of material or another material that constitutes the glass substrate. It may be formed.

  By the anti-glare treatment as described above, irregularities having an order of μm or more are formed on the surface of the glass substrate, for example. The “antiglare property” of the glass substrate is represented by the maximum height roughness Rz of the glass substrate obtained by a measurement method according to JIS B 0601 2001, and may be in the range of 0.3 μm to 10 μm, for example.

  The glossiness of the glass substrate after the antiglare treatment is, for example, 70% or less, preferably 65% or less, and more preferably 60% or less.

  In addition, in this application, the "glossiness" of a glass substrate means the value obtained by the measuring method based on JISZ8741.

  Since the glossiness is a numerical value reflecting the reflectance, the glossiness is lowered by improving the antireflection performance even if the shape of the substrate surface is the same.

  Through the above treatment, a glass substrate having antiglare properties can be obtained.

(Step S120)
Next, the glass substrate prepared in step S110 described above is exposed to a processing gas containing a fluorine compound, and an etching process for the glass substrate is performed. This process is performed on the surface of the glass substrate that has been antiglare treated in step S110. In addition, the etching process is performed in an atmospheric atmosphere at normal pressure.

  This step is performed in order to form fine irregularities on the surface of the glass substrate, for example, on the order of 1 nm to 200 nm. Due to the presence of these fine irregularities, antireflection properties are imparted to the glass substrate.

  As described above, the etching amount of the glass substrate etched by this treatment is on the order of nm and is extremely fine. Therefore, it should be noted that the etching process hardly affects the antiglare property developed in the glass substrate in step S110.

  The etching process is performed in the range of 250 ° C to 650 ° C. The treatment temperature is preferably in the range of 275 ° C to 600 ° C, and more preferably in the range of 300 ° C to 600 ° C.

  The kind of fluorine compound used for the etching treatment is not particularly limited as long as it is a gas containing hydrogen fluoride at the time of etching on the glass surface. As a raw material of the processing gas containing a fluorine compound, for example, hydrogen fluoride and / or trifluoroacetic acid may be used. Hydrogen fluoride and trifluoroacetic acid are preferable from the viewpoint of safety because they are non-explosive. Trifluoroacetic acid is thermally decomposed by the temperature of the glass surface to generate hydrogen fluoride.

  The processing gas may contain a carrier gas in addition to the gaseous fluorine compound. The carrier gas is not limited to this, but, for example, nitrogen and / or argon is used.

  The concentration of the fluorine compound in the processing gas is not particularly limited as long as the surface of the glass substrate is appropriately etched. The concentration of the fluorine compound in the processing gas is, for example, in the range of 0.1 vol% to 10 vol%, preferably in the range of 0.3 vol% to 8 vol%, and in the range of 0.5 vol% to 5 vol%. It is more preferable.

  You may implement the etching process of a glass substrate in the state which conveyed the glass substrate. In this case, faster processing is possible.

  FIG. 2 shows a configuration example of a processing apparatus for performing an etching process on a glass substrate while the glass substrate 180 is conveyed. In the following description, the case where the gaseous fluorine compound is hydrogen fluoride gas will be described as an example.

  As shown in FIG. 2, the processing apparatus 100 includes an injector 110 and a transport unit 150.

  The transport means 150 can transport the glass substrate 180 placed on the top in the horizontal direction (X direction) as indicated by an arrow F201.

  The injector 110 is disposed above the conveying means 150 and the glass substrate 180.

  The injector 110 has a plurality of slits 115, 120, and 125 that serve as flow paths for processing gas. That is, the injector 110 is provided along the vertical direction (Z direction) so as to surround the first slit 115 provided in the central portion along the vertical direction (Z direction). A second slit 120 and a third slit 125 provided along the vertical direction (Z direction) so as to surround the second slit 120 are provided.

  One end (upper part) of the first slit 115 is connected to a hydrogen fluoride gas source (not shown), and the other end (lower part) of the first slit 115 is oriented toward the glass substrate 180. The Similarly, one end (upper part) of the second slit 120 is connected to a carrier gas source (not shown), and the other end (lower part) of the second slit 120 is oriented toward the glass substrate 180. Is done. One end (upper part) of the third slit 125 is connected to an exhaust system (not shown), and the other end (lower part) of the third slit 125 is oriented toward the glass substrate 180.

  When performing the etching process of the glass substrate 180 using the processing apparatus 100, first, from the hydrogen fluoride gas source (not shown), through the first slit 115, in the direction of the arrow F 205. Hydrogen fluoride gas is supplied. A carrier gas such as nitrogen is supplied from a carrier gas source (not shown) through the second slit 120 in the direction of arrow F210. These gases move in the horizontal direction (X direction) along the arrow F215, and are then discharged to the outside of the processing apparatus 100 through the third slit 125 by the exhaust system.

  Note that a carrier gas may be simultaneously supplied to the first slit 115 in addition to the hydrogen fluoride gas.

  The glass substrate 180 is conveyed by the conveyance means 150 in the direction of arrow F201.

  When the glass substrate 180 passes under the injector 110, the glass substrate 180 comes into contact with the processing gas (hydrogen fluoride gas + carrier gas) supplied from the first slit 115 and the second slit 120. Thereby, the surface of the glass substrate 180 is etched.

  Note that the processing gas supplied to the surface of the glass substrate 180 moves as indicated by an arrow F215 and is used for an etching process, and then moves as indicated by an arrow F220 and is connected to an exhaust system. It is discharged to the outside of the processing apparatus 100 via 125.

  By using the processing apparatus 100, it is possible to carry out surface etching with a processing gas while conveying a glass substrate. In this case, the processing efficiency can be improved as compared with a method of performing an etching process using a reaction vessel. In addition, when the processing apparatus 100 is used, the etching process can be applied to a large glass substrate.

  Here, the supply speed of the processing gas to the glass substrate 180 is not particularly limited. The supply speed of the processing gas may be, for example, in the range of 5 SLM to 1000 SLM (volume per minute (liter) in standard state gas).

  Moreover, the conveyance speed of the glass substrate 180 is 1 m / min-20 m / min, for example.

  Moreover, the passage time of the glass substrate 180 through the injector 110 is in the range of 1 second to 120 seconds, preferably in the range of 5 seconds to 60 seconds, and more preferably in the range of 5 seconds to 30 seconds. By setting the passage time of the glass substrate 180 through the injector 110 to 120 seconds or less, a rapid etching process can be performed.

  Here, the “passing time of the injector 110” means a time for a certain region of the glass substrate 180 to pass the distance S in FIG. Note that the distance S is a slit on the most upstream side of the slit on the most upstream side of the injector 110 (slit 125 in the example of FIG. 2) with respect to the conveyance direction of the glass substrate 180 (slit 125 in the example of FIG. 2). ) Is determined by the distance between the downstream ends.

  As described above, by using the processing apparatus 100, it is possible to perform an etching process on the glass substrate in the transported state.

  Note that the processing apparatus 100 illustrated in FIG. 2 is merely an example, and the glass substrate may be etched using a processing gas containing hydrogen fluoride gas using another apparatus. For example, in the processing apparatus 100 of FIG. 2, the glass substrate 180 moves relative to the stationary injector 110. However, on the contrary, the injector may be moved in the horizontal direction with respect to the stationary glass substrate. Alternatively, both the glass substrate and the injector may be moved in directions opposite to each other.

  In addition, in the processing apparatus 100 of FIG. 2, the injector 110 has a total of three slits 115, 120, and 125. However, the number of slits is not particularly limited. For example, the number of slits may be two. In this case, one slit may be used for supplying a processing gas (a mixed gas of carrier gas and hydrogen fluoride gas), and another slit may be used for exhaust.

  Further, in the processing apparatus 100 of FIG. 2, the second slit 120 of the injector 110 is disposed so as to surround the first slit 115, and the third slit 125 is the first slit 115 and the second slit 120. Is provided so as to surround. However, instead of this, the first slit, the second slit, and the third slit may be arranged in a line along the horizontal direction (X direction). In this case, the processing gas moves along the surface of the glass substrate along one direction, and then is exhausted through the third slit.

  Through the processes of (Step S110) and (Step S120), a glass having both antiglare property and antireflection property can be produced.

  Next, examples of the present invention will be described.

(Example 1)
Antireflection glass having antiglare properties was produced by the following method, and the characteristics thereof were evaluated.

(Anti-glare treatment)
First, antiglare treatment was performed on one surface of a 3 mm thick glass substrate (soda lime glass).

  Anti-glare treatment was performed by wet treatment. Specifically, the antiglare treatment was performed by immersing one surface of the glass substrate in a hydrofluoric acid solution at room temperature for 30 minutes. As a result, an “antiglare substrate according to Example 1” was obtained.

  The glossiness of the surface of the antiglare substrate according to Example 1 was measured. A gloss checker IG-331 (manufactured by Horiba Seisakusho) was used to measure the glossiness, and the 60 ° glossiness was measured based on JIS Z8741. As a result of the measurement, the 60 ° glossiness of the antiglare substrate according to Example 1 was 56%, and it was confirmed that significant antiglare property was obtained.

(Etching process)
Next, etching using HF gas was performed using the antiglare substrate according to Example 1 processed as described above. For the etching process, the processing apparatus 100 shown in FIG. 2 was used.

  In the processing apparatus 100, a mixed gas of hydrogen fluoride gas and nitrogen gas was supplied to the first slit 115 at a flow rate of 34 cm / second. The supply amount of hydrogen fluoride gas is 1.0 SLM (volume per minute in standard state gas (liter)), and the supply amount of nitrogen gas is 31.0 SLM (volume per minute in standard state gas). (Liter)). The mixed gas was supplied in a state heated to 150 ° C.

  Further, nitrogen gas was supplied to the second slit 120 at a flow rate of 34 cm / second. The temperature of nitrogen gas was 150 ° C., and the supply amount of nitrogen gas was 10 SLM.

  The concentration of hydrogen fluoride gas with respect to the total supply gas is 2.4 vol%.

  The exhaust amount from the third slit 125 was twice the supply amount of the supply gas.

  The conveyance speed of the anti-glare substrate according to Example 1 was 2 m / min, and the anti-glare substrate according to Example 1 was conveyed while being heated to 580 ° C. The temperature of the antiglare substrate according to Example 1 is a value measured using a radiation thermometer immediately before supplying the processing gas.

  The etching processing time (the time for the glass substrate to pass the distance S in FIG. 2) was about 10 seconds.

  After this treatment, a large number of irregularities on the order of nm were formed on the etched surface of the antiglare substrate according to Example 1. Hereinafter, the obtained anti-glare substrate according to Example 1 is referred to as “glass according to Example 1”.

(Evaluation)
Using the glass according to Example 1, the antireflection property was evaluated.

  The antireflection property of the glass was evaluated by measuring the total light transmittance. The total light transmittance was carried out based on JIS K7361-1 using a haze meter HZ-2 (Suga Test Machine). The light source was a C light source.

  As a result of the measurement, the total light transmittance Tt of the glass according to Example 1 was 94.9%.

  In addition, when the same measurement was performed with respect to the glass substrate before implementing both an anti-glare process and an etching process, the total light transmittance Tt was 91.7%. Further, when the same measurement was performed on the antiglare substrate according to Example 1, the total light transmittance Tt was 92.4%. From this result, the transmittance increase value of the glass according to Example 1 with respect to the untreated glass substrate is 3.2%. Further, the transmittance increase value ΔTt of the glass according to Example 1 with respect to the antiglare substrate according to Example 1 is 2.5%.

  Thus, it was found that the glass according to Example 1 has significantly higher antireflection properties than the untreated glass substrate and the antiglare substrate according to Example 1.

  Next, the 60 ° glossiness of the glass according to Example 1 was measured by the method described above. As a result of the measurement, the 60 ° glossiness of the glass according to Example 1 was 30%.

  Next, the roughness of the treated surface of the glass according to Example 1 was measured based on JIS B0601: 2001. As a result of measurement using a scanning probe microscope (SPI3800N: manufactured by SII Nanotechnology), the arithmetic average roughness Ra of the surface of the glass according to Example 1 was 70 nm. Moreover, the maximum height roughness Rz of the glass surface according to Example 1 was 0.486 μm. Note that these measurements were carried out with the number of acquired data being 1024 × 1024 in a 2 μm × 2 μm region of the sample.

  Thus, it was confirmed that the glass according to Example 1 has anti-glare properties and significantly low reflectivity.

(Example 2)
Antireflection glass having antiglare properties was produced by the following method, and the characteristics thereof were evaluated.

(Anti-glare treatment)
First, antiglare treatment was performed on one surface of a 3 mm thick glass substrate (soda lime glass).

  The antiglare treatment was performed by sandblasting one surface of the glass substrate. As a result, an “antiglare substrate according to Example 2” was obtained.

  The glossiness of the surface of the antiglare substrate according to Example 2 was measured by the method described above. As a result of the measurement, the 60 ° glossiness was 32%, and it was confirmed that significant antiglare property was obtained.

(Etching process)
Next, using the antiglare substrate according to Example 2, an etching process using HF gas was performed in the same manner as in Example 1 described above. However, in Example 2, the temperature of the antiglare substrate according to Example 2 was set to 530 ° C. Other conditions are the same as in the first embodiment.

  After this etching process, a number of irregularities on the order of nm were formed on the processed surface of the antiglare substrate according to Example 2. Hereinafter, the obtained glass substrate is referred to as “glass according to Example 2”.

(Evaluation)
Using the glass according to Example 2, the total light transmittance Tt was measured by the method described above. As a result of the measurement, the total light transmittance Tt of the glass according to Example 2 was 92.7%.

  In addition, when the same measurement was performed with respect to the glass substrate before implementing both an anti-glare process and an etching process, the total light transmittance Tt was 91.7%. Further, when the same measurement was performed on the antiglare substrate according to Example 2, the total light transmittance Tt was 91.5%. From this result, the transmittance increase value ΔTt of the glass according to Example 2 with respect to the untreated glass substrate is 1.0%. Further, the transmittance increase value ΔTt of the glass according to Example 2 with respect to the antiglare substrate according to Example 2 is 1.2%.

  Thus, it was found that the glass according to Example 2 has significantly higher antireflection properties than the untreated glass substrate and the antiglare substrate according to Example 2.

  Next, the 60 ° glossiness of the glass according to Example 2 was measured by the method described above. As a result of the measurement, the 60 ° glossiness of the glass according to Example 2 was 21%.

  Next, the roughness of the treated surface of the glass according to Example 2 was measured by the method described above. As a result of the measurement, the arithmetic average roughness Ra of the surface of the glass according to Example 2 was 99 nm. Further, the maximum height roughness Rz of the glass surface according to Example 2 was 0.679 μm.

  Thus, it was confirmed that the glass according to Example 2 has antiglare properties and significantly low reflectivity.

(Example 3)
By the same method as in Example 1, anti-glare glass having antiglare properties was produced, and its characteristics were evaluated.

  However, in Example 3, the etching process was performed under the following conditions.

(Etching process)
Etching with HF gas was performed using a glass substrate that was anti-glare treated in the same manner as in Example 1 (hereinafter referred to as “anti-glare substrate according to Example 3”). For the etching process, the processing apparatus 100 shown in FIG. 2 was used.

  In the processing apparatus 100, a mixed gas of hydrogen fluoride gas and nitrogen gas was supplied to the first slit 115 at a flow rate of 34 cm / second. The supply amount of hydrogen fluoride gas is 1.5 SLM (volume per minute in standard state gas (liter)), and the supply amount of nitrogen gas is 30.5 SLM (volume per minute in standard state gas). (Liter)). The mixed gas was supplied in a state heated to 150 ° C.

  Further, nitrogen gas was supplied to the second slit 120 at a flow rate of 34 cm / second. The temperature of nitrogen gas was 150 ° C., and the supply amount of nitrogen gas was 10 SLM.

  The concentration of hydrogen fluoride gas with respect to the total supply gas is 3.6 vol%.

  The exhaust amount from the third slit 125 was twice the supply amount of the supply gas.

  The conveyance speed of the anti-glare substrate according to Example 3 was 2 m / min, and the anti-glare substrate according to Example 3 was conveyed while being heated to 350 ° C.

  The etching processing time (the time for the glass substrate to pass the distance S in FIG. 2) was about 10 seconds.

  After this treatment, a large number of irregularities on the order of nm were formed on the treated surface of the antiglare substrate according to Example 3. Hereinafter, the obtained anti-glare substrate according to Example 3 is referred to as “glass according to Example 3”.

(Evaluation)
Using the glass according to Example 3, the total light transmittance Tt was measured by the method described above. As a result of the measurement, the total light transmittance Tt of the glass according to Example 3 was 94.2%.

  In addition, when the same measurement was performed with respect to the glass substrate before implementing both an anti-glare process and an etching process, the total light transmittance Tt was 91.7%. Further, when the same measurement was performed on the antiglare substrate according to Example 3, the total light transmittance Tt was 92.4%. From this result, the transmittance increase value of the glass according to Example 3 with respect to the untreated glass substrate is 2.5%. Further, the transmittance increase value ΔTt of the glass according to Example 3 with respect to the antiglare substrate according to Example 3 is 1.8%.

  Thus, it was found that the glass according to Example 3 has significantly higher antireflection properties than the untreated glass substrate and the antiglare substrate according to Example 3.

  Next, the 60 ° glossiness of the glass according to Example 3 was measured by the method described above. As a result of the measurement, the 60 ° glossiness of the glass according to Example 3 was 49%.

  Next, the roughness of the treated surface of the glass according to Example 3 was measured by the method described above. As a result of the measurement, the arithmetic average roughness Ra of the surface of the glass according to Example 3 was 78 nm. Moreover, the maximum height roughness Rz of the glass surface according to Example 3 was 0.475 μm.

  Thus, it was confirmed that the glass according to Example 3 has antiglare properties and significantly low reflectivity.

(Comparative Example 1)
By the same method as in Example 1, anti-glare glass having antiglare properties was produced, and its characteristics were evaluated.

  However, in Comparative Example 1, the etching process was performed under the following conditions.

(Etching process)
Etching with HF gas was performed using a glass substrate that was anti-glare treated in the same manner as in Example 1 (hereinafter referred to as “anti-glare substrate according to Comparative Example 1”). For the etching process, the processing apparatus 100 shown in FIG. 2 was used.

  In the processing apparatus 100, a mixed gas of hydrogen fluoride gas and nitrogen gas was supplied to the first slit 115 at a flow rate of 34 cm / second. The supply amount of hydrogen fluoride gas is 1.5 SLM (volume per minute in standard state gas (liter)), and the supply amount of nitrogen gas is 30.5 SLM (volume per minute in standard state gas). (Liter)). The mixed gas was supplied in a state heated to 150 ° C.

  Further, nitrogen gas was supplied to the second slit 120 at a flow rate of 34 cm / second. The temperature of nitrogen gas was 150 ° C., and the supply amount of nitrogen gas was 10 SLM.

  The concentration of hydrogen fluoride gas with respect to the total supply gas is 3.6 vol%.

  The exhaust amount from the third slit 125 was twice the supply amount of the supply gas.

  The conveyance speed of the anti-glare board | substrate which concerns on the comparative example 1 was 2 m / min, and the anti-glare board | substrate which concerns on the comparative example 1 was conveyed in the state heated at 200 degreeC.

  The etching processing time (the time for the glass substrate to pass the distance S in FIG. 2) was about 10 seconds.

  Hereinafter, the obtained antiglare substrate according to Comparative Example 1 is referred to as “glass according to Comparative Example 1”.

(Evaluation)
Using the glass according to Comparative Example 1, the total light transmittance Tt was measured by the method described above. As a result of the measurement, the total light transmittance Tt of the glass according to Example 3 was 92.4%.

  In addition, when the same measurement was performed with respect to the glass substrate before implementing both an anti-glare process and an etching process, the total light transmittance Tt was 91.7%. Further, when the same measurement was performed on the antiglare substrate according to Comparative Example 1, the total light transmittance Tt was 92.4%. From this result, the transmittance increase value of the glass according to Comparative Example 1 with respect to the untreated glass substrate is 0.7%. The transmittance increase value ΔTt of the glass according to Comparative Example 1 with respect to the antiglare substrate according to Comparative Example 1 is 0.0%.

  Thus, in the glass according to Comparative Example 1, the transmittance increase width was less than 1% as compared with the untreated glass substrate and the anti-glare substrate according to Comparative Example 1.

  Next, the 60 ° glossiness of the glass according to Comparative Example 1 was measured by the method described above. As a result of the measurement, the 60 ° glossiness of the glass according to Comparative Example 1 was 54%.

  Next, the roughness of the treated surface of the glass according to Comparative Example 1 was measured by the method described above. As a result of the measurement, the arithmetic average roughness Ra of the surface of the glass according to Comparative Example 1 was 66 nm. Moreover, the maximum height roughness Rz of the surface of the glass which concerns on the comparative example 1 was 0.449 micrometer.

  As described above, it was confirmed that the glass according to Comparative Example 1 has antiglare property, but low reflectivity is insufficient.

  In addition, when the etching treatment was performed under the same conditions as in Example 3 using ordinary soda lime glass having no antireflection property, and the same measurement was performed before and after that, the total light transmittance Tt before the etching treatment was obtained. Was 91.7%, the total light transmittance Tt after the etching treatment was 94.2%, and the transmittance increase value was 2.5%. Therefore, it was confirmed that the glass in the examples of the present application has antiglare properties and significantly low reflectivity.

  Table 1 below summarizes the glass manufacturing conditions and evaluation results in Examples 1 to 3 and Comparative Example 1.

  The present invention is used, for example, for glass products having high light transmittance, such as glass for building materials, glass for automobiles, glass for displays, optical elements, glass for solar cells, show window glass, optical glass, and eyeglass lenses. can do.

DESCRIPTION OF SYMBOLS 100 Processing apparatus 110 Injector 115 1st slit 120 2nd slit 125 3rd slit 150 Conveying means 180 Glass substrate

Claims (12)

A method for producing glass having antireflection properties,
(A) providing a glass substrate having an anti-glare surface;
(B) contacting a treatment gas containing a fluorine compound with the surface of the glass substrate in a temperature range of 250 ° C. to 650 ° C. under normal pressure and atmospheric atmosphere;
The manufacturing method of the glass which has antireflective property characterized by having.   2. The method for producing an antireflective glass according to claim 1, wherein hydrogen fluoride and / or trifluoroacetic acid are contained as a raw material of the processing gas.   The method for producing an antireflective glass according to claim 1 or 2, wherein the concentration of the hydrogen fluoride gas in the processing gas is in the range of 0.1 vol% to 10 vol%.   The method for producing an antireflective glass according to any one of claims 1 to 3, wherein the processing gas further contains nitrogen and / or argon.   The arithmetic average roughness Ra of the surface of the glass substrate after the step (b) is 10 nm or more, and the maximum height roughness Rz is 0.3 μm or more. 5. A method for producing an antireflective glass according to any one of 4 above.   In the step (b), the glass substrate is brought into contact with the processing gas in a transported state, wherein the glass having antireflection properties according to any one of claims 1 to 5 is manufactured. Method. An injector is disposed on the upper or lower portion of the glass substrate,
The method for producing an antireflective glass according to any one of claims 1 to 6, wherein the processing gas is discharged from the injector toward the glass substrate.   The method for producing an antireflective glass according to claim 7, wherein the glass substrate passes under the injector between 1 second and 120 seconds.   The difference ΔTt between the total light transmittance of the glass substrate after the step (b) and the total light transmittance of the glass substrate before the step (b) after the step (a) is 1% or more. The method for producing an antireflective glass according to claim 1, wherein the glass has antireflection properties.   The step (a) includes performing at least one selected from the group consisting of a blasting process, a wet process, a coating process, and an embossing process on a glass substrate. The manufacturing method of the glass which has antireflection property as described in any one of 1 thru | or 9.   The glass having antireflection properties according to any one of claims 1 to 10, wherein the glossiness of the surface of the glass substrate after the step (b) is 70% or less. Method.   The method for producing an antireflective glass according to any one of claims 1 to 11, wherein the glass is a panel for a solar cell or a panel for a display.

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