WO2007108514A1

WO2007108514A1 - Glass plate having antibacterial film, method of producing the same and article having the glass plate

Info

Publication number: WO2007108514A1
Application number: PCT/JP2007/055915
Authority: WO
Inventors: Hidemasa Yoshida; Tsuyoshi Otani; Akira Fujisawa
Original assignee: Nippon Sheet Glass Company, Limited
Priority date: 2006-03-22
Filing date: 2007-03-22
Publication date: 2007-09-27
Also published as: JP2007254192A

Abstract

It is intended to provide a glass plate having an antibacterial film which is equipped with an antibacterial film scarcely showing an interference color due to reflection. It is also intended to provide a method of producing a glass plate, which is a large-sized glass plate having an antibacterial film formed thereon and shows an improved mechanical durability of the antibacterial film, in a large amount at a low cost. This glass plate having an antibacterial film is produced by forming an antibacterial film having a film thickness of 2 nm or more but not more than 100 nm on a glass plate either directly or via an undercoat film. The antibacterial film is formed by the heat decomposition method which comprises supplying a film-forming gas onto the surface of a glass plate, which has been maintained at such a temperature as allowing the decomposition of the film-forming gas or higher, or onto the surface of a glass ribbon in the course of producing a glass plate.

Description

Specification

TECHNICAL FIELD The present invention relates to a glass plate with an antibacterial film, a manufacturing method thereof, and an article having the glass plate.

The present invention relates to a glass plate with an antibacterial film and a method for producing the same, and further relates to an article having the glass plate.

Background art

[0002] The need for a comfortable living space is extremely high. In a hot and humid environment, breeding of bacteria, microorganisms, etc. becomes active. Such bacteria, microorganisms, etc. often have adverse effects on the human body, and in order to effectively inhibit their reproduction, plate-like antibacterial members that can be used as components of living spaces and inexpensive, large-scale There is a need for a method for producing such parts that can be produced.

[0003] For example, Japanese Patent Application Laid-Open No. 2001-72438 discloses an antibacterial processed plate glass material that can form an antibacterial effect by forming a coating film made of a resin composition containing acid titanium or the like as an antibacterial agent. ing. However, the antibacterial strength plate glass material is selected from roll coating, dip coating, spray coating, electrostatic coating, electrodeposition coating, wire coating, flow coating, doctor coating, etc. Since the coating film was formed by this method, the thickness of the coating film became 10-50 / ζ πι and a micron unit, and a film thinner than these could not be formed uniformly. In this specification, a film formed on the surface of a member in order to impart antibacterial properties to the member is referred to as an “antibacterial film”. As the antibacterial film, metal materials such as silver, zinc and copper and photocatalytic materials such as titanium oxide are used.

[0004] Titanium oxide is widely used as a photocatalytic material because of its high photocatalytic activity and excellent chemical stability. When titanium oxide is irradiated with ultraviolet rays, electrons and holes are generated.

, It shows a photoinduced decomposition reaction and a photoinduced hydrophilic reaction. Antibacterial tiles using these reactions have already been commercialized.

[0005] WO94Z11092 pamphlet discloses a technique in which powdered titanium oxide titanium is sintered on a glass plate. Although this technique can be used to obtain a plate-like antibacterial member, when coating particulate glass titanium oxide on a glass plate, the acidity is reduced. Tan particles aggregate to inevitably increase the particle size of titanium oxide. When the particle diameter of the acid titanium is increased, the thickness of the antibacterial film containing the acid titanium is increased. As a result, there was a problem that the reflectance of the antibacterial film increased and the interference color of the reflection became conspicuous.

[0006] In addition, the method of International Publication No. 94Z11092 pamphlet has another problem that the antibacterial film is low in mechanical durability because the antibacterial film is formed using powdered titanium oxide. Furthermore, it is not only difficult to form an antibacterial film uniformly on a large-area glass substrate, but it is also necessary to carry out a baking process and a coating process. It is unsuitable for continuous mass production of large area glass plates.

[0007] Further, the method for producing a nitrogen-doped titanium oxide film disclosed in WO 01/10552 is an invention relating to a method for producing a glass plate having an antibacterial film formed on the surface thereof, and a sputtering method. After forming the TiO film with the atmosphere containing ammonia and nitrogen

2

It is a method of baking treatment. However, the method disclosed in the pamphlet of International Publication No. 01Z10552 can obtain a plate-like antibacterial member, but requires a large-scale vacuum apparatus, and the deposition apparatus is often very expensive. . In addition, there is a problem in that the firing process is required, and the number of manufacturing steps increases and the manufacturing cost increases. As described above, the method for producing a nitrogen-doped titanium oxide film disclosed in WO 01/10552 is not suitable for continuous mass production of a large area glass plate.

Disclosure of the invention

[0008] The present invention has been completed by paying attention to the above-described problems. Its purpose is to provide a glass plate with an antibacterial film, which has an antibacterial film, which has produced interference colors of reflection. It is another object of the present invention to provide a method for manufacturing a large-sized glass plate with an antibacterial film formed thereon, which is a large area glass plate with improved mechanical durability.

[0009] The glass plate with an antibacterial film of the present invention is a glass plate with an antibacterial film comprising an antibacterial film directly or via a base film on the glass plate, and the film thickness of the antibacterial film is 2 nm or more and lOOnm or less. is there.

[0010] preferred, embodiment Nio, Te, the antimicrobial performance of the antimicrobial film is antimicrobial product technology Council irradiation film adhesion method 10 μ WZcm ² of the ultraviolet light quantity irradiation 24 hours based on the stipulated Antibacterial performance that reduces the number of Staphylococcus aureus or Escherichia coli after irradiation to less than lZio 0 relative to the number of bacteria before irradiation.

[0011] In a preferred embodiment, the antibacterial performance of the antibacterial film is such that the yellow grapes are irradiated with ultraviolet light having a light intensity of 10 μWZcm ² for 8 hours based on the light irradiation film adhesion method defined by the Antibacterial Product Technical Council. Antibacterial performance that reduces the number of cocci or E. coli to 1Z100 or less with respect to the number of bacteria before light irradiation.

[0012] Preferably, according to the embodiment, the antibacterial performance of the antibacterial film is based on a light irradiation film adhesion method stipulated by the Antibacterial Product Technical Council, and after irradiating a white fluorescent lamp with an amount of lOOOLx for 24 hours. Antibacterial performance to reduce the number of Staphylococcus aureus or Escherichia coli to 1Z100 or less with respect to the number of bacteria before light irradiation.

[0013] Preferably, according to the embodiment, the antibacterial performance of the antibacterial film is yellow after irradiating a white fluorescent lamp with a light quantity of 500Lx for 24 hours based on the light irradiation film adhesion method defined by the Antibacterial Product Technical Council. Antibacterial performance that reduces the number of Staphylococcus or Escherichia coli to 1Z100 or less compared to the number of bacteria before light irradiation.

[0014] Preferably, according to the embodiment, the antibacterial performance of the antibacterial film is yellow after irradiating a white fluorescent lamp with a light quantity of 250Lx for 24 hours based on the light irradiation film adhesion method defined by the Antibacterial Product Technical Council. Antibacterial performance that reduces the number of Staphylococcus or Escherichia coli to 1Z100 or less compared to the number of bacteria before light irradiation.

In a preferred embodiment, the antibacterial performance is an antibacterial performance that reduces the number of Staphylococcus aureus or Escherichia coli to 1 Z 10,000 or less.

In a preferred embodiment, the film thickness of the antibacterial film is 5 nm or more and 80 nm or less, and in a further preferred embodiment, the film thickness of the antibacterial film is more than 25 nm and less than 70 nm.

In a preferred embodiment, the main component of the antibacterial film is one selected from the group force consisting of titanium oxide, nitrogen-doped titanium oxide, titanium oxynitride, and titanium nitride power.

[0018] In a preferred embodiment, the main component of the antibacterial film is nitrogen-doped titanium oxide.

[0019] According to another aspect of the present invention, a method for producing a glass plate with an antibacterial film is provided. this For the manufacturing method, the antibacterial film is formed by a thermal decomposition method.

[0020] Preferably, for the embodiment, the film forming gas is supplied to the surface of the glass plate in which the antibacterial film is maintained at a temperature higher than the temperature at which the film forming gas is decomposed or the glass ribbon surface in the glass plate manufacturing process. To form.

In a preferred embodiment, the film forming gas contains a titanium-containing compound, a nitrogen-containing compound, and an oxidizing gas.

[0022] Preferably, for the embodiment, the film-forming gas further includes a reaction inhibitor that suppresses a chemical reaction between the titanium-containing compound and the nitrogen-containing compound.

[0023] In a preferred embodiment, the nitrogen-containing compound is ammonia.

[0024] Preferably, in the embodiment, the acidic gas is oxygen.

[0025] Preferably, according to the embodiment, the molar specific power of the acidic gas such as oxygen to the nitrogen-containing compound such as ammonia in the coating forming gas is 0.05 or more. is there.

[0026] Preferably, in the embodiment, the reaction inhibitor is salt hydrogen.

[0027] In a preferred embodiment, the thermal decomposition method is a CVD method performed in a nose for forming a molten glass ribbon into a plate shape in a glass manufacturing process by a float method.

[0028] According to yet another aspect of the present invention, a glass window for a building is provided. They have the above glass plate with antibacterial film. For example, living windows or glass windows in medical facilities, indoor glass, etc. are provided.

[0029] According to still another aspect of the present invention, a glass partition in a building is provided. They have the above glass plate with antibacterial film.

[0030] According to still another aspect of the present invention, furniture is provided. They have the above-mentioned glass plate with an antibacterial film. For example, glass tables, glass shelves, glass showcases or glass food cases are provided.

[0031] According to yet another aspect of the invention, a glass window for a transport machine is provided. They have the above glass plate with antibacterial film. For example, vehicle, ship or aircraft glass windows are provided. [0032] According to still another aspect of the present invention, an information display glass panel is provided. They have the above glass plate with antibacterial film. For example, display panels and touch panels are provided.

[0033] According to the present invention, since the thickness of the antibacterial film is set in a range of 2 nm or more and lOOnm or less, generation of reflection interference colors is suppressed even when a titanium compound having a relatively high refractive index is used. An antibacterial film-coated glass plate comprising an antibacterial film is provided.

[0034] Further, according to the present invention, in the manufacturing process of the float glass, a large area is obtained by performing a pyrolysis method in a bath for forming a molten glass ribbon into a plate shape. There is provided a method for producing a glass plate with an antibacterial film in which the mechanical durability of the antibacterial film is enhanced in large quantities at a low cost.

[0035] Further, according to the present invention, an article having an antibacterial film-coated glass is provided.

Brief Description of Drawings

[0036] FIG. 1 is a cross-sectional view showing an example of a glass plate with an antibacterial film of the present invention. FIG. 1 (a) shows an example in which the antibacterial film is directly formed on the glass plate. Shows an example in which a base film is interposed between the glass plate and the antibacterial film.

[Fig. 2] This is a schematic diagram of the equipment used for the on-line CVD method.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to these embodiments.

[0038] In the present specification, the term "antibacterial" means that the growth of bacteria or microorganisms attached to an object is suppressed, and the viable number of bacteria or microorganisms decreases with the passage of time. The term “main component” means a component that occupies 50% by weight or more. The term “light irradiation film adhesion method defined by the Antibacterial Product Technology Council” means the light irradiation film adhesion method (2003 version) established by the Antibacterial Product Technology Council. Antibacterial performance is evaluated based on the conditions stipulated in the dressing law. This measurement method was one of the most common measurement methods for assessing the antibacterial properties of products for those skilled in the art until JIS R1702: 2006 was issued after the basic application of this application was filed. .

FIG. 1 is a schematic cross-sectional view illustrating two forms of the antibacterial film-coated glass plate 4 according to the present invention. . In the glass plate according to the present invention, as a first embodiment, an antibacterial film 2 is formed on the glass plate 1 as shown in FIG.

[0040] Further, as the second embodiment, as shown in Fig. 1 (b), it is preferable to configure the base film 3 so as to have one or more layers between the glass plate 1 and the antibacterial film 2. This base film preferably has a role such as an alkali barrier function. When the glass plate 1 is a glass plate containing an alkali component, for example, when the alkali component moves to the antibacterial membrane 2 during the film formation process of the antibacterial membrane 2, the crystallinity of the antibacterial membrane deteriorates and the antibacterial performance deteriorates. In that case, if the base film is sandwiched, adverse effects due to the movement of the alkali component can be prevented.

[Preferable Range of Film Thickness] When the film thickness of the antibacterial film is large, a reflection interference color is exhibited, and the appearance quality is remarkably deteriorated. On the other hand, if the film thickness is too small, the reflection interference color is suppressed, but the antibacterial performance deteriorates. For this reason, the thickness of the antibacterial film is preferably in the range of 2 nm to lOOnm and more preferably in the range of 5 nm to 80 nm. Furthermore, the range of more than 20 nm and less than 70 nm is most preferable.

[0042] [Antimicrobial performance]

The antibacterial performance of the antibacterial film of the present invention is as follows: after the irradiation with ultraviolet light of 10 μWZcm ² for 24 hours in the light irradiation film adhesion method (2003 version) established by the Antibacterial Product Technical Council. Antibacterial performance that reduces the number of Staphylococcus aureus or Escherichia coli to 1Z100 or less with respect to the number of bacteria before light irradiation is preferred. More preferably, the antibacterial performance is to reduce the number of Staphylococcus aureus or Escherichia coli after irradiation with ultraviolet light of 10 / z WZcm ² for 8 hours to 1Z100 or less with respect to the number of bacteria before light irradiation. . In addition, according to the light irradiation film adhesion method (2003 version) established by the Antibacterial Product Technology Council, the number of Staphylococcus aureus or Escherichia coli after 24 hours of irradiation with a white fluorescent lamp with a light intensity of lOOOLx is measured before light irradiation. Antibacterial performance that reduces the number of bacteria to 1Z100 or less is preferable. More preferably, the antibacterial performance is to reduce the number of Staphylococcus aureus or Escherichia coli after irradiation with a white fluorescent lamp with a light quantity of 500 Lx for 24 hours to 1Z100 or less with respect to the number of bacteria before light irradiation. More preferably, a staphylococcus aureus or Escherichia coli after being irradiated with a white fluorescent lamp with a light intensity of 25 OLx for 24 hours. Antibacterial performance that reduces the number to less than ΐΖΐοο against the number of bacteria before light irradiation. Since antibacterial performance evaluation is a test using microorganisms, the evaluation test error is larger than other physical property evaluations. If the number of bacteria after light irradiation is 1Z100 or less (the sterilization rate is 99% or more), it can be said that there is clearly an advantageous effect on antibacterial performance that is not within the error range. In Japan Antibacterial Performance Evaluation, if the bacteria survival rate is 1% or less (the number of bacteria is reduced to 1Z100 or less), the difference between antibacterial processed products and unprocessed products Can be judged significantly. As a more preferable range, the number of bacteria after light irradiation is 1 Ziooo or less. As a more preferable range, the number of bacteria after light irradiation is 1Z10000 or less.

[0043] In the antibacterial performance evaluation, it is necessary to set the intensity of the ultraviolet light to be irradiated and the illuminance of the white fluorescent lamp according to the usage conditions. The intensity of ultraviolet light and the illuminance of white fluorescent lamps are typified by the following locations.

Ultraviolet light WZcm ² · · 'In the daytime room, about 1.5m away from the window where sunlight enters.

Fluorescent lamp lOOOLx · · · A place about lm above the indoor floor where only the fluorescent lamp is lit. The intensity of the ultraviolet light in the fluorescent lamp lOOOLx is, 4 / z WZcm ² about.

Fluorescent light 500Lx · · · Indoor floor with only fluorescent light on. The intensity of ultraviolet light in fluorescent lamp 1000 Lx is about 2 / z WZcm ² .

[0044] The bacteria to be reduced by the present invention is not particularly limited, but the present invention can be used for the following fungi. Examples include bacteria of Gram-positive bacteria (S. aureus, Bacillus, etc.) or Gram-negative bacteria (E. coli, Salmonella, etc.), fungi such as fungi, mushrooms, yeasts, other viruses, and protists.

[0045] [Antimicrobial component]

The main component of the antibacterial film of the present invention is preferably one selected from the group power of titanium oxide, nitrogen-doped titanium oxide, titanium oxynitride, and titanium nitride power. This is because an antibacterial film containing these as main components has high antibacterial performance and excellent chemical stability.

[0046] In particular, the main component is preferably nitrogen-doped acid titanium. In particular, nitrogen-doped acid Titanium fluoride is a photocatalytic material that responds to the light of visible light, so it is preferable in that it can use light in the visible light region that is often contained in sunlight and fluorescent lamps.

[0047] [Raw material]

(Raw material of antibacterial film)

The raw material for the antibacterial membrane of the present invention contains at least one titanium-containing compound, at least one nitrogen-containing compound, and at least one acid gas. is required.

[0048] The titanium-containing compound is preferably a titanium chloride, a titanium alkoxide or a titanium chelate compound. These titanium-containing compounds are preferably in the form of a gas or liquid at room temperature, and when they are liquid at room temperature, the lower boiling point is preferable. These preferable titanium-containing compounds can be vaporized as they are or by heating a little, and can be used as components of the raw material gas. In addition, a titanium-containing compound that sublimes even if it is solid at room temperature, or a titanium-containing compound that can be dissolved in an organic solvent such as alcohol or toluene can be used.

[0049] Examples of such titanium-containing compounds include, for example, tetrasalt-titanium (TiCl), titanium ethoxy

Four

(Ti (OCH)), Titanium Isoproxide (Ti (OCH)), Titanium Normal Butoxide (Ti

2 5 4 3 7 4

(OC H)), titanium acetyl cetate ((C HO) Ti (CHO)), etc.

4 9 4 3 7 2 2 5 7 2 2

The In particular, tetrasalt 匕 titanium (TiCl), titanium isoproxide (Ti (OC H)), or titanium

4 3 7 4

N-butanol (Ti (OCH)) is preferably used.

4 9 4

[0050] As the nitrogen-containing compound, ammonia (NH), amines, and hydrazine derivatives are preferable.

Three

It can be exemplified as appropriate. Among these, ammonia easily liquefies by compression and is a gas at room temperature and normal pressure, and is particularly preferable in that it can be obtained in a large amount at a preferred low cost because it can be easily introduced into the raw material gas. . Aminyahydrazine derivatives are excellent in that they can easily produce high quality films because of their high reactivity. On the other hand, it is disadvantageous in that it is expensive.

[0051] As the acidic gas, it is preferable to use oxygen (O 2). Carbon dioxide (CO 2), acid

Compounds containing oxygen such as carbon dioxide (CO) and water vapor (H 2 O) can be used. Water (H

twenty two

When liquid raw materials such as O) and esters are used, facilities for vaporizing the liquid raw materials are required. In addition, the amount of vaporization tends to be unstable. It is preferable to use a gas raw material whose supply amount is easy to control. Of these, it is particularly preferable to use oxygen. Air can also be used. When air is used as an acidic gas, nitrogen (N) contained in the air can act as a reaction diluent.

2

[0052] When ammonia is used as the nitrogen-containing compound and oxygen is used as the acidic gas, the molar ratio of oxygen to ammonia (O ZNH ratio) is preferably 0.05 or more. Ammo

twenty three

This is because the crystallinity of the film can be improved by setting the molar ratio of oxygen to air to 0.05 or more. The recombination of the generated electrons and holes is thought to occur at the crystal defect site. Therefore, by improving the crystallinity, that is, by reducing the defect sites of the crystal, the rate of successful recombination with electrons can be reduced and antibacterial properties can be enhanced.

[0053] The raw material of the antibacterial membrane of the present invention preferably further contains a reaction inhibitor that suppresses a chemical reaction between the titanium-containing compound and the nitrogen-containing compound.

[0054] As the reaction inhibitor, it is preferable to use salt hydrogen.

[0055] When titanium tetrachloride is used as the titanium-containing compound and ammonia is used as the nitrogen-containing compound, the gas phase reaction may proceed before the raw material gas reaches the glass plate. As this gas phase reaction proceeds, a solid reaction product is generated in the raw gas piping. This reaction product may block the piping. In addition, this reaction product is transported to the surface of the glass plate by the flow of the raw material gas, is taken into the film to be formed, and causes defects such as pinholes. In order to prevent this gas phase reaction, it is preferable to use hydrogen chloride as reaction suppression.

[0056] [Method for producing glass plate with antibacterial film]

The manufacturing method of the antibacterial film is not particularly limited, but a known thermal decomposition method such as a thermal CVD method or a spray method is used. In addition, a fine powder of the antibacterial film is attached to the glass surface, and then the entire glass. Examples thereof include a method of agglomerating the fine powder by heating. Further, after the fine powder is agglomerated, the antibacterial film may be crystal-grown by the thermal decomposition method using the agglomerated fine powder as a nucleus. Among these, the thermal decomposition method, particularly the thermal CVD method, can easily form a film with high mechanical durability.

[0057] The film formation by the thermal CVD method uses, for example, a glass plate as a substrate and a glass having a predetermined size. This can be done by heating the glass plate and spraying a gaseous raw material on the surface of the heated glass plate.

Specifically, this can be performed as follows. The glass plate is transported on a mesh belt and passed through a tunnel-shaped heating furnace. The glass plate is conveyed into a heating furnace and heated to a temperature at which the film-forming gas decomposes (hereinafter abbreviated as “film-forming gas decomposition temperature”). When the glass plate is heated to the film forming gas decomposition temperature, the source gas is supplied into the heating furnace. The source gas reacts with the heat of the surface of the glass plate, and an antibacterial film having antibacterial action is formed on the glass plate.

[0059] The film-forming gas decomposition temperature is preferably 500 ° C or higher from the viewpoint of obtaining high crystallinity and high film formation rate. That is, it is preferable to form an antibacterial film on the surface of a glass plate at 500 ° C or higher. TiNCl, TiCl · ηΝΗ, etc. when the temperature is below 500 ° C

This is because a low temperature product of 4 3 is easily formed.

[0060] Further, in the thermal CVD method, in the glass plate manufacturing process, the glass plate is heated at a high temperature in the step of forming the glass melt into the glass plate or in the slow cooling step after the glass plate is formed. It is preferable to utilize that. This is because if a raw material gas is supplied onto a high-temperature glass plate, a thin film can be formed without using a separate heating facility. In addition, in this way, a thin film can be formed at high speed on a glass plate having a large area, and a glass plate with a thin film can be produced for applications that require a large area such as buildings, vehicles, and display panels. it can. As described above, the method of forming a film on a high-temperature glass plate in the middle of the manufacturing process is called an online CVD method.

[0061] (In-bus CVD method)

The above-described process of forming the glass melt and the glass plate is performed in a molten tin tank (referred to as a float bath) in the glass plate manufacturing process by the float process. The glass melt melted in the melting furnace (called the float kiln) flows into the float bath. The glass melt is drawn into a long strip without interruption and is called a glass ribbon.

[0062] A method in which the online CVD method is performed in a float bath is called an in-bus CVD method. In addition to the advantages described above, the intra-CVD method has the following advantages. First, the atmosphere inside the float bath is controlled so that air does not enter. Therefore, pinhole etc. It is possible to suppress defects. The temperature of the glass ribbon in the float bath is very high. The temperature depends on the strength of the glass ribbon. In the case of ordinary soda lime silicate glass, the temperature is, for example, in the range of 650 to 1150 ° C.

[0063] Within such a temperature range, the crystallinity of the thin film having antibacterial performance can be improved and the antibacterial performance can be improved. In addition, since the raw material gas exhibits sufficient reactivity, a thin film having a sufficient thickness of antibacterial performance can be easily formed on the glass ribbon without lowering the conveyance speed of the glass ribbon. As a result, productivity can be expected to increase, and it becomes possible to manufacture a large number of glass plates with antibacterial films at low cost.

[0064] Fig. 2 shows an embodiment of an apparatus for forming a film on a glass ribbon by the in-bus CVD method in the float method. As shown in FIG. 2, in this apparatus, the surface force of the glass ribbon 10 that flows out from the float kiln 11 into the float bath 12 and moves in a strip shape on the molten tin 15 is also separated by a predetermined distance, and a predetermined number of coaters 16 Is arranged in the float bath. In FIG. 2, three coaters 16a, 16b and 16c are shown. The number of coaters can be appropriately designed according to the design of the membrane configuration. From these coaters, raw materials for the antibacterial film having an antibacterial action and the base film are supplied in a gas state, and each thin film is continuously formed on the glass ribbon 10. If a plurality of coaters are used, a thin film can be laminated on the glass ribbon 10. The temperature of the glass ribbon is adjusted by a heater and a cooler (not shown) arranged in the float bath so as to reach a predetermined temperature just before the coater 16. The glass ribbon 10 on which the thin film has been formed is pulled up by a roller 17 and fed into a rare (slow cooling kiln) 13. The glass plate slowly cooled by the layer 13 is cut into a glass plate of a predetermined size by a general-purpose cutting device (not shown).

[0065] (Rare CVD method)

Further, as described above, the on-line CVD method can also be performed in a slow cooling step (called “rare”) after being formed into a glass plate. In this case, the raw material gas is introduced at the inlet of the rare (slow cooling kiln) and Z or inside the rare. Hereinafter, this method is referred to as a rare-layer CVD method. Although the glass ribbon near the rare entrance or the rare entrance in the rare is at a lower temperature than in the bath, it has a sufficiently high temperature for the film formation reaction. The rare CVD method has the following features, unlike the chemical CVD method. First of all, it is not suitable for bus CVD method. For example, a raw material whose reaction rate is too high at the glass ribbon temperature of the CVD method in the bath, or a raw material that may have an unfavorable effect on the float bath can be used. It can also be applied to glass plate manufacturing processes that do not have a float bath. For example, it can be applied to a glass plate manufacturing process by a roll-out method, and a plate glass, a netted glass, and a wire glass having an antibacterial film having an antibacterial action can be manufactured.

Example

[0066] Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.

[0067] (Examples 1 to 12, comparative example)

A non-alkali glass plate having a thickness of 0.7 mm was cut into a square having a side of 10 cm, washed, and then dried. On one surface of this glass plate, a nitrogen-doped titanium oxide film was formed by atmospheric pressure CVD using a transfer furnace of an atmospheric pressure thermal CVD apparatus. In particular

Is as follows.

[0068] The above glass plate was placed on a mesh belt and conveyed in the above furnace to heat the glass plate. In the region in the furnace where the temperature of the glass plate reached about 850 ° C, a nitrogen-doped titanium oxide film was formed by supplying a source gas to the surface of the glass plate. This source gas includes titanium tetrachloride (TiCl), oxygen (O), ammonia (NH), and hydrogen chloride as a reaction inhibitor.

4 2 3

(HC1) was employed, and a gas diluted with nitrogen gas to a predetermined concentration was used. A nitrogen-doped titanium oxide film was formed by adjusting the concentration of the source gas and the conveying speed.

[0069] (Examples 13 to 14)

Using the equipment shown in Fig. 2, a thin film was formed on the surface of the glass ribbon by the CVD method in the bus. Specifically, it is as follows.

[0070] A glass melt melted in a float kiln and controlled at a temperature of 1150-: L 100 ° C was allowed to flow into the float bath. In the float bath, the glass melt was formed into a glass ribbon while being cooled. The glass ribbon was molded to a thickness of 4. Omm. The first coater (16a in Fig. 2) formed an SiO film with a thickness of 50 nm on the glass ribbon as a base film.

2

. Thereafter, a raw material gas was sprayed from the second coater (16b in FIG. 2) to form a thin film. [0071] In Example 13, the raw material gases include tetrasalt 匕 titanium (TiCl), ethyl acetate (CHO

4 4 8

) And a gas diluted to a predetermined concentration with nitrogen gas was used. Source gas concentration and

2

A titanium oxide film was formed by adjusting the conveyance speed.

In Example 14, a nitrogen-doped titanium oxide film was formed using the same source gas as in Examples 1 to 12 and the comparative example.

[0073] (Antimicrobial film thickness)

The cross section of the glass plate on which the thin film was formed was measured by observing it with a scanning electron microscope (SEM).

[0074] (Interference color)

The presence or absence of interference colors was judged by visual observation.

[0075] (Antimicrobial performance)

The antibacterial properties of the obtained films were evaluated by the light irradiation film adhesion method established by the Antibacterial Product Technical Council.

[0076] (Antimicrobial performance test 1)

Based on the light irradiation film adhesion method stipulated by the antibacterial product technology council above, using a black light fluorescent lamp (FL20S 'BLB'JET20W manufactured by Toshiba Lighting & Technology Corporation), an ultraviolet intensity meter (UVR-2 manufactured by Topcon, light receiving unit UD— The ultraviolet intensity measured in 36) was adjusted to 10 WZcm ² and irradiated with ultraviolet rays for 24 hours under the conditions of 95% humidity and 25 ° C. The test bacteria were evaluated using Staphylococcus aureus NBRC12732. Moreover, about Example 3, 5, 8-14, evaluation using Escherichia coli (Escherichiacoli N BRC3972) as a test microbe was also implemented.

[0077] In any of the thin films of Examples 1 to 14 and the comparative example, the number of Staphylococcus aureus after 24 hours of ultraviolet irradiation is reduced to 1Z100 or less, and has good antibacterial properties. In addition, in the thin films of Examples 3, 5, and 8 to 14, the number of E. coli after 24 hours of ultraviolet irradiation was reduced to 1Z100 or less, and had good antibacterial properties.

[0078] (Antimicrobial performance test 2)

For Examples 3, 5, and 8-14, the UV intensity was adjusted to 10 / z WZcm ² and the irradiation time of ultraviolet rays was set to 8 hours, as in (Antibacterial performance test 1) above. Test gave. The test strain was evaluated using Staphylococcus aureus NBRC12732.

[0079] In any of the thin films of Examples 3, 5, and 8 to 14, the number of bacteria after 8 hours of ultraviolet irradiation was reduced to 1Z100 or less and had good antibacterial properties.

[0080] (Antimicrobial performance test 3)

For Examples 3, 5, and 8-14, based on the light irradiation film adhesion method defined by the Antibacterial Product Technical Council, using a white fluorescent lamp, adjusting the illuminance to lOOOLx, the white fluorescent lamp The test was conducted in the same manner as the above (Antibacterial performance test 1) except that the irradiation time was 24 hours. The test bacteria were evaluated using Staphylococcus aureus NBRC12732 and Escherichia coli NBRC3972.

[0081] In any of the thin films of Examples 3, 5, and 8 to 14, the number of bacteria after 24 hours of ultraviolet irradiation was reduced to 1Z100 or less and had good antibacterial properties.

[0082] (Antimicrobial performance test 4)

For Examples 3, 5, and 9-14, based on the light irradiation film adhesion method defined by the Antibacterial Product Technical Council, the white fluorescent lamp was adjusted so that the illuminance was 500 Lx. The test was conducted in the same manner as the above (Antibacterial performance test 1) except that the irradiation time was 24 hours. The test bacteria were evaluated using Staphylococcus aureus NBRC12732.

[0083] In any of the thin films of Examples 3, 5, and 9 to 14, the number of bacteria after 24 hours of ultraviolet irradiation decreased to 1Z100 or less, and had good antibacterial properties.

[0084] (Antimicrobial performance test 5)

For Examples 4, 9, and 12-13, based on the light irradiation film adhesion method defined by the Antibacterial Product Technical Council, the white fluorescent lamp was adjusted so that the illuminance was 250 Lx, and the white fluorescent lamp was irradiated. The test was conducted in the same manner as (Antibacterial performance test 1) except that the time was 24 hours. The test bacteria were evaluated using Staphylococcus aureus NBRC12732.

[0085] In any of the thin films of Examples 4, 9, and 12 to 13, the number of bacteria after 24 hours of ultraviolet irradiation was reduced to 1Z100 or less and had good antibacterial properties. [0086] The above results are shown in the table.

[0087] [Table 1]

[0088] As shown in the table, the thin films of Examples 1 to 14 had a thickness in the range of 5 to 80 nm, and thus had no interference color. On the other hand, an interference color occurred in the comparative thin film having a thickness of 150 nm.

Industrial applicability

[0089] The glass plate with an antibacterial film of the present invention is different from conventional ones in the fields of glass windows for buildings, glass windows for transportation machinery, glass panels for information display, etc. It has a great utility value in that it can provide a glass plate with an antibacterial film with improved mechanical durability.

Claims

The scope of the claims

[1] An antibacterial film-attached glass plate comprising an antibacterial film directly or via a base film on a glass plate, wherein the antibacterial film has a film thickness of 2 nm or more and lOOnm or less.

[2] The antibacterial performance of the antibacterial membrane is the number of Staphylococcus aureus or Escherichia coli after irradiation with ultraviolet light of 10 μWZcm ² for 24 hours based on the light irradiation film adhesion method established by the Antibacterial Product Technical Council. The glass plate with an antibacterial film according to claim 1, which has an antibacterial performance that reduces the number of bacteria to 1Z100 or less with respect to the number of bacteria before light irradiation.

[3] The antibacterial performance of the antibacterial film is the number of Staphylococcus aureus or Escherichia coli after irradiation with ultraviolet light of 10 μWZcm ² for 8 hours based on the light irradiation film adhesion method established by the Antibacterial Product Technical Council. 2. The glass plate with an antibacterial film according to claim 1, which has antibacterial performance that reduces the number of bacteria before light irradiation to 1Z100 or less.

[4] The antibacterial performance of the antibacterial membrane reduces the number of Staphylococcus aureus or Escherichia coli after irradiation with a white fluorescent lamp with a light quantity of lOOOLx for 24 hours to 1Z100 or less compared to the number of bacteria before light irradiation. The glass plate with an antibacterial film according to claim 1, which has antibacterial performance.

[5] The antibacterial performance of the antibacterial membrane reduces the number of Staphylococcus aureus or Escherichia coli after irradiation with a white fluorescent lamp with a light quantity of 500Lx for 24 hours to 1Z100 or less with respect to the number of bacteria before light irradiation. The glass plate with an antibacterial film according to claim 1, which has antibacterial performance.

[6] The antibacterial performance of the antibacterial membrane reduces the number of Staphylococcus aureus or Escherichia coli after irradiation with a white fluorescent lamp with a light intensity of 250 Lx for 24 hours to 1Z100 or less with respect to the number of bacteria before light irradiation. The glass plate with an antibacterial film according to claim 1, which has antibacterial performance.

7. The glass plate with an antibacterial film according to claim 1, wherein the antibacterial performance is an antibacterial performance that reduces the number of Staphylococcus aureus or Escherichia coli to 1Z10000 or less.

8. The glass plate with an antibacterial film according to claim 1, wherein the antibacterial film has a thickness of 5 nm or more and 80 nm or less.

[9] The glass plate with an antibacterial film according to [1], wherein the film thickness of the antibacterial film is more than 25 nm and less than 70 nm.

[10] The glass with an antibacterial film according to claim 1, wherein the main component of the antibacterial film is one selected from the group force of titanium oxide, nitrogen-doped titanium oxide, titanium oxynitride, and titanium nitride power. Board.

11. The glass plate with an antibacterial film according to claim 10, wherein a main component of the antibacterial film is nitrogen-doped titanium dioxide.

12. The method for producing a glass plate with an antibacterial film according to claim 1, wherein the antibacterial film is formed by a thermal decomposition method.

[13] The antibacterial film is formed by supplying a film-forming gas to a glass plate surface maintained at a temperature higher than a temperature at which the film-forming gas decomposes or a glass ribbon surface in the glass plate manufacturing process. The manufacturing method of the glass plate with an antibacterial film of description.

14. The method for producing a glass plate with an antibacterial film according to claim 13, wherein the film-forming gas contains a titanium-containing compound, a nitrogen-containing compound, and an oxidizing gas.

[15] The glass plate with an antibacterial film according to [14], wherein the film-forming gas further includes a reaction inhibitor that suppresses a chemical reaction between the titanium-containing compound and the nitrogen-containing compound. Production method.

16. The method for producing a glass plate with an antibacterial film according to claim 14, wherein the nitrogen-containing compound is ammonia.

17. The method for producing a glass plate with an antibacterial film according to claim 14, wherein the acidic gas is oxygen.

18. The method for producing a glass plate with an antibacterial film according to claim 14, wherein a molar ratio of the oxidizing gas to the nitrogen-containing compound in the coating forming gas is 0.05 or more.

19. The method for producing a glass plate with an antibacterial film according to claim 15, wherein the reaction inhibitor is salty hydrogen.

[20] The glass plate with an antibacterial film according to [12], wherein the thermal decomposition method is a CVD method performed in a bath for forming a glass ribbon in a molten state into a plate shape in a glass manufacturing process by a float method. Manufacturing method.

[21] A glass window of a building having the glass plate with an antibacterial film according to claim 1.

[22] A glass partition in a building having the glass plate with an antibacterial film according to claim 1.

[23] A furniture comprising the glass plate with an antibacterial film according to claim 1.

[24] A glass window for a transport machine, comprising the glass plate with an antibacterial film according to claim 1. [25] An information display glass panel comprising the antibacterial film-coated glass plate according to [1].