WO2017119279A1

WO2017119279A1 - Glass member

Info

Publication number: WO2017119279A1
Application number: PCT/JP2016/087892
Authority: WO
Inventors: 林　英明; 啓明岩岡
Original assignee: 旭硝子株式会社
Priority date: 2016-01-04
Filing date: 2016-12-20
Publication date: 2017-07-13
Also published as: JP2017122012A

Abstract

A glass member having a glass substrate, wherein: the glass substrate has a first surface and a second surface; a coating is provided to the first surface of the glass substrate; the coating comprises, from the side close to the glass substrate, an undercoat layer that includes a silicon oxide and a heat shielding layer that includes a tin oxide; when a 10 mm sample square cut from the glass member is heat treated for 7 minutes and 30 seconds at 670°C in air atmosphere, the sheet resistance increase is within 20%; and in the glass member, the visible light transmittance T_v measured according to ISO 9050:2003 is 78% or higher, the haze level is 10% or higher, and the shading coefficient SC is 0.90 or lower.

Description

Glass member

The present invention relates to a glass member, and more particularly to a glass member including a glass substrate having a thermal barrier coating.

In recent years, glass houses have attracted attention as a medium- to large-scale horticultural facility used for growing crops in various countries. A glass house is more durable and airtight than a greenhouse, and various facilities can be introduced inside, so that a highly productive cultivation environment can be realized (for example, Patent Document 1).

WO2006 / 098285

Patent Document 1 described above describes that a heat insulating multilayer film is formed on a transmissive substrate (glass substrate) and used as a glass member for a glass house.

However, the characteristic required for glass members for glass houses is not limited to heat insulation.

For example, in a glass house, a shade may be formed in the glass house by a frame material for a skeleton that supports the glass member. Since such shade can adversely affect the growth of plants and the like, it is preferable to suppress it as much as possible. However, with the glass member described in Patent Document 1, it is difficult to deal with such a “shade” problem.

Thus, a glass member more suitable for application to an actual glass house is still demanded.

This invention is made | formed in view of such a background, and it aims at providing the glass member suitable for application to a glass house compared with the past in this invention.

In the present invention, a glass member having a glass substrate,
The glass substrate has a first surface and a second surface;
A coating is placed on the first surface of the glass substrate,
The coating is from the side close to the glass substrate,
An undercoat layer containing silicon oxide;
A thermal barrier layer containing tin oxide;
Have
When the sample cut into a 10 mm square is heat-treated at 670 ° C. for 7 minutes and 30 seconds in an air atmosphere, the sheet resistance increase rate is within 20%.
When the glass member is measured from the glass substrate side,
ISO9050: measured according to 2003 the visible light transmittance _{T v} is not less 78% or more,
The haze rate is 10% or more,
When the solar heat acquisition rate measured according to ISO 9050: 2003 is g value (%), and the value represented by the following formula (1) is the shielding coefficient SC,

SC = g value / 0.88 (1) Formula
A glass member having the SC of 0.90 or less is provided.

In the present invention, it is possible to provide a glass member suitable for application to a glass house as compared with the conventional case.

It is sectional drawing which showed schematically the structural example of the glass member by one Embodiment of this invention. It is sectional drawing which showed schematically the structural example of another glass member by one Embodiment of this invention. It is sectional drawing which showed roughly the structural example of the another glass member by one Embodiment of this invention. It is sectional drawing which showed roughly the structural example of the another glass member by one Embodiment of this invention. It is the flowchart which showed roughly an example of the manufacturing method of the glass member by one Embodiment of this invention.

Generally, a glass member applied to a glass house is subjected to a tempering process or a semi-strengthening process in order to prevent a strong wind caused by a typhoon or the like and a crack caused by a fall of a kite or a pebble. Tempering is achieved by applying compressive stress to the surface of the glass. As an example of the strengthening treatment, air cooling strengthening for rapidly cooling the surface of the glass heated to the vicinity of the softening point, and dipping the glass in a molten salt containing the first alkali metal ions, the second alkali metal contained in the glass Examples include chemical strengthening that exchanges ions with the surface of the glass. Air-cooling strengthening is excellent in that a large-area glass plate can be tempered efficiently at a relatively low cost, and post-strengthening treatment can be carried out on coated glass. When glass with a coating is tempered by air cooling, the coating needs to have heat resistance that does not change even when the glass member is reheated to near the softening point of the glass.

The glass member in the present invention has relatively good heat resistance. More specifically, the glass member in the present invention has a feature that the sheet resistance increase rate is within 20% when a sample cut into 10 mm square is heat-treated at 670 ° C. for 7 minutes and 30 seconds in an air atmosphere.

For this reason, in the glass member in the present invention, it is possible to significantly suppress the problem that the coating changes in quality during the reheating accompanying the air cooling strengthening and the heat shielding property of the coating is lowered.

In the present application, the sheet resistance increase rate (%) is represented by (sheet resistance of the sample after heat treatment−sheet resistance of the sample before heat treatment) / (sheet resistance of the sample before heat treatment) × 100.

The glass member according to the present invention, ISO9050: measured according to 2003 the visible light transmittance _{T v} is 78% or more. The visible light transmittance is preferably 79% or more, more preferably 80% or more, and further preferably 81% or more.

In this case, sufficient sunlight can be taken into the glass house. Therefore, when such a glass member is applied to a glass house, it becomes possible to significantly promote plant growth.

The glass member in the present invention has a shielding coefficient SC of 0.90 or less when measured from the glass substrate side. Therefore, when such a glass member is applied to a glass house, the invasion of heat from the sun can be significantly avoided. In particular, in the summer, it is possible to suppress solar heat from entering the glass house, thereby reducing the cooling cost and the like, and significantly reducing the running cost of the glass house.

The shielding coefficient SC is preferably 0.85 or less, more preferably 0.80 or less, and further preferably 0.76 or less.

Furthermore, when measured from the glass substrate side, the glass member in the present invention has a haze ratio of 10% or more and high light diffusibility. When such a glass member having high light diffusibility is applied to a glass house, it is possible to significantly suppress the shadow of the frame material constituting the framework of the glass house from being projected onto the plants in the glass house. . As a result, it becomes possible to promote favorable growth of the plant.

Note that the haze ratio is preferably 15% or more, more preferably 18% or more, and further preferably 25% or more. Further, the haze ratio is preferably 90% or less, more preferably 80% or less, and still more preferably 60% or less.

Due to the above characteristics, the present invention can provide a glass member more suitable for application to a glass house than in the prior art.

(First configuration)
Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

FIG. 1 schematically shows a cross section of a glass member (hereinafter referred to as “first glass member”) according to an embodiment of the present invention.

As shown in FIG. 1, the first glass member 100 includes a glass substrate 110 and layers disposed on both sides of the glass substrate 110.

More specifically, the glass substrate 110 has a first surface 112 and a second surface 114, and the undercoat layer 120 and the heat shielding layer 130 are formed on the first surface 112 in the order closer to the glass substrate 110. Is arranged. On the other hand, an antifouling layer 180 is disposed on the second surface 114 of the glass substrate 110.

The first glass member 100 has a first side 102 and a second side 104, the first side 102 corresponds to the side of the thermal barrier layer 130, and the second side 104 is an antifouling layer. This corresponds to the 180 side.

The glass substrate 110 is made of, for example, soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, quartz glass, borosilicate glass, alkali-free glass, or the like.

In particular, when it is desired to increase the visible light transmittance, the glass substrate 110 is made of a highly transmissive glass (for example, soda lime silicate glass) in which the content of the iron component is suppressed.

The thickness of the glass substrate 110 is, for example, in the range of 1.5 mm to 6 mm, and preferably in the range of 2 mm to 5 mm.

The undercoat layer 120 has a role as an alkali barrier layer that suppresses a decrease in heat shielding performance due to diffusion of sodium in the glass substrate into the heat shielding layer while increasing the haze ratio of the heat shielding layer.

The undercoat layer 120 is composed of a layer containing silicon oxide. The amount of silicon oxide contained in the undercoat layer 120 is preferably 50% by mass or more. For example, the undercoat layer 120 may be composed of a silicon oxide layer (SiO ₂ ), a silicon oxycarbide layer (SiOC), or the like.

Here, the surface of the undercoat layer 120 preferably has an arithmetic average roughness Ra in the range of 1 nm to 150 nm. The arithmetic average roughness Ra is more preferably 10 nm to 100 nm, 20 nm to 90 nm, and 40 to 80 nm. In this case, the haze ratio of the first glass member 100 can be significantly increased.

However, when the surface of the undercoat layer 120 has large unevenness, the alkali component tends to diffuse from the glass substrate 110 toward the heat shield layer 130, and the characteristics of the heat shield layer 130 may be deteriorated. In order to prevent this, for example, an alkali barrier layer made of silica containing substantially no carbon may be added between the undercoat layer 120 and the heat shield layer 130. Thereby, the problem of such deterioration of the heat shield layer 130 can be suppressed.

The undercoat layer 120 has a thickness of 15 nm to 150 nm, for example. The thickness is more preferably 20 nm to 120 nm and 25 nm to 100 nm.

The heat shield layer 130 has a role of suppressing heat input by the light 108 incident on the first glass member 100 from the second side 104.

The heat shield layer 130 is composed of a layer containing tin oxide. The amount of tin oxide contained in the heat shield layer 130 is preferably 50% by mass or more. For example, the thermal barrier layer 130 may be made of tin oxide doped with fluorine and / or antimony. In this case, the dopant content is preferably in the range of 0.0001 to 0.09 in terms of a dopant atom / tin atom molar ratio.

The heat shield layer 130 has a thickness of 100 nm to 1000 nm, for example. More preferably, the thickness is 120 nm to 800 nm, 140 nm to 700 nm, 150 nm to 500 nm.

The antifouling layer 180 has a role of preventing the transparency of the first glass member 100 from being deteriorated due to dust or dust adhering to the second side 104 of the first glass member 100.

The antifouling layer 180 has a thickness of 10 nm to 150 nm. Further, the antifouling layer 180 may have a surface roughness (arithmetic average roughness Ra) of 1 nm to 13 nm.

The antifouling layer may be composed of, for example, a tin oxide layer or a silica layer. The antifouling layer 180 is not an essential layer and may be omitted.

In the first glass member 100, the first side 102 and / or the second side 104 do not necessarily have to be flat surfaces, and these may be curved surfaces.

When the first glass member 100 is applied to a glass house, the first glass member 100 is arranged so that the first side 102 is inside the glass house and the second side 104 is outside the glass house. The Accordingly, the sunlight 108 is incident from the second side 104 of the first glass member 100 toward the glass house.

Here, the first glass member 100 has a feature that when the sample cut into a 10 mm square is heat-treated at 670 ° C. for 7 minutes and 30 seconds in an air atmosphere, the sheet resistance increase rate is within 20%. The sheet resistance increase rate is preferably 15% or less, and more preferably 10% or less. Thereby, the heat-shielding fall by the high temperature of the 1st glass member 100 can be suppressed significantly.

The first glass member 100, ISO 9050: measured according to 2003 the visible light transmittance _{T v} has the feature that is 78% or more. For this reason, in the 1st glass member 100, sufficient sunlight can be taken in in a glass house. As a result, in the glass house including the first glass member 100, it is possible to significantly promote the growth of plants.

Further, the first glass member 100 has a haze ratio measured from the second side 104 toward the first side 102 of 15% or more. For this reason, the glass house provided with the 1st glass member 100 is excellent in light diffusibility, and can suppress the above-mentioned "shade" problem significantly.

Further, in the first glass member 100, the shielding coefficient SC measured from the second side 104 toward the first side 102 is 0.90 or less. Therefore, in the glass house provided with the 1st glass member 100, favorable heat-shielding property is acquired and the running cost of a glass house can be suppressed significantly.

(Second configuration)
In FIG. 2, the cross section of another glass member by one Embodiment of this invention is shown typically.

As shown in FIG. 2, another glass member (hereinafter referred to as a “second glass member”) 200 according to an embodiment of the present invention includes a glass substrate 210 and layers disposed on both sides of the glass substrate 210. And have.

More specifically, the glass substrate 210 has a first surface 212 and a second surface 214, and the undercoat layer 220 and the first shielding layer are formed on the first surface 212 in the order closer to the glass substrate 210. A thermal layer 230 and a second thermal barrier layer 240 are disposed. On the other hand, an antifouling layer 280 is disposed on the second surface 214 of the glass substrate 210.

The second glass member 200 has a first side 202 and a second side 204, the first side 202 corresponds to the second thermal barrier layer 240 side, and the second side 204 is It corresponds to the antifouling layer 280 side.

Here, the glass substrate 210 may have the same configuration as the glass substrate 110 in the first glass member 100 described above.

Further, the undercoat layer 220 may be made of the same material as the undercoat layer 120 in the first glass member 100 described above. However, unlike the undercoat layer 120 in the first glass member 100, the undercoat layer 220 has a substantially flat surface. This is because the second glass member 200 can obtain a suitable haze ratio even if the surface of the undercoat layer 220 is not particularly roughened.

The undercoat layer 220 has a thickness of 10 nm to 60 nm, for example. The thickness is preferably in the range of 15 nm to 50 nm, and more preferably in the range of 20 nm to 45 nm.

The first heat shield layer 230 is composed of a layer containing tin oxide. The amount of tin oxide contained in the first heat shield layer 230 is preferably 50% by mass or more. For example, the first heat shield layer 230 may be made of tin oxide (undoped).

The first heat shield layer 230 has a thickness of 100 nm to 500 nm, for example. The thickness is preferably in the range of 120 nm to 400 nm, and more preferably in the range of 140 to 350 nm.

On the other hand, the second heat shield layer 240 may have the same configuration as the heat shield layer 230 in the first glass member 100 described above. For example, the second heat shielding layer 240 may be made of tin oxide or the like doped with fluorine and / or antimony.

The second heat shield layer 240 has a thickness of 100 nm to 500 nm, for example. The thickness is preferably in the range of 120 nm to 400 nm, and more preferably in the range of 140 to 350 nm.

The antifouling layer 280 may have the same configuration as the antifouling layer 180 of the first glass member 100. Further, the antifouling layer 280 may be omitted.

The second glass member 200 has the same characteristics as the first glass member 100 described above. That is, the second glass member 200 is
When the sample cut into 10 mm square was heat-treated at 670 ° C. for 7 minutes and 30 seconds in an air atmosphere, the sheet resistance increase rate was within 20%,
Visible light transmittance _Tv is 78% or more,
The haze rate is 15% or more,
The shielding coefficient SC is 0.90 or less.

Therefore, also in the second glass member 200, the same effect as that of the first glass member 100 described above can be obtained. That is, when the 2nd glass member 200 is applied to a glass house, the heat-shielding fall by high temperature can be suppressed significantly. In addition, it is possible to incorporate enough sunlight into the glass house, and the good light diffusibility significantly suppresses the above-mentioned “shade” problem and significantly reduces the running cost of the glass house. The effect that can be obtained.

(Third configuration)
In FIG. 3, the cross section of another glass member by one Embodiment of this invention is typically shown.

As shown in FIG. 3, still another glass member (hereinafter referred to as “third glass member”) 300 according to an embodiment of the present invention is disposed on a glass substrate 310 and on both sides of the glass substrate 310. Each layer.

More specifically, the glass substrate 310 has a first surface 312 and a second surface 314, and the first undercoat layer 350, the first surface 312, and the first surface 312 are arranged in the order closer to the glass substrate 310. Two undercoat layers 320, a first heat shield layer 330, and a second heat shield layer 340 are disposed. On the other hand, an antifouling layer 380 is disposed on the second surface 314 of the glass substrate 310.

Note that the first undercoat layer 350 and the antifouling layer 380 may be omitted.

The third glass member 300 has a first side 302 and a second side 304, the first side 302 corresponds to the second thermal barrier layer 340 side, and the second side 304 is It corresponds to the antifouling layer 380 side.

Here, the glass substrate 310 may have the same configuration as the glass substrate 110 in the first glass member 100 described above.

On the other hand, the first undercoat layer 350 is composed of, for example, a layer containing titanium oxide. The amount of titanium oxide contained in the first undercoat layer 350 is preferably 50% by mass or more. For example, the first undercoat layer 350 may be composed of a titanium oxide layer (TiO ₂ ) or the like.

The first undercoat layer 350 has a thickness of 3 nm to 20 nm, for example. The thickness is preferably in the range of 5 nm to 15 nm.

The second undercoat layer 320 is composed of a layer containing silicon oxide. The amount of silicon oxide contained in the second undercoat layer 320 is preferably 50% by mass or more. For example, the second undercoat layer 320 may be composed of a silicon oxide layer (SiO ₂ ) or the like.

The second undercoat layer 320 has a substantially flat surface, and has a thickness of 10 nm to 60 nm, for example. The thickness is preferably in the range of 15 nm to 50 nm, and more preferably in the range of 20 nm to 45 nm.

The first heat shield layer 330 is composed of a layer containing tin oxide. The amount of tin oxide contained in the first heat shield layer 330 is preferably 50% by mass or more. For example, the first heat shield layer 330 may be made of tin oxide or the like doped with fluorine and / or antimony.

The first heat shield layer 330 has a thickness of 100 nm to 500 nm, for example. The thickness is preferably in the range of 120 nm to 400 nm, and more preferably in the range of 140 to 350 nm.

On the other hand, the second heat shield layer 340 is also composed of a layer containing tin oxide. The amount of tin oxide contained in the second heat shield layer 340 is preferably 50% by mass or more. For example, the second heat shielding layer 340 may be made of tin oxide or the like doped with fluorine and / or antimony.

Here, the second heat shield layer 340 has a feature that the carrier concentration is higher than that of the first heat shield layer 330. For example, the first thermal barrier layer 330 has a carrier concentration in the range of 1 × 10 ²⁰ cm ⁻³ to 4 × 10 ²⁰ cm ⁻³ . In contrast, the second thermal barrier layer 340 has a carrier concentration in the range of 3 × 10 ²⁰ cm ⁻³ to 6 × 10 ²⁰ cm ⁻³ .

The second heat shielding layer 340 has a thickness of 100 nm to 500 nm, for example. The thickness is preferably in the range of 120 nm to 400 nm, and more preferably in the range of 140 to 350 nm.

The antifouling layer 380 may have the same configuration as the antifouling layer 180 of the first glass member 100. Further, the antifouling layer 380 may be omitted.

The third glass member 300 also has the same characteristics as the first glass member 100 and the second glass member 200 described above. That is, the third glass member 300 is
When the sample cut into 10 mm square was heat-treated at 670 ° C. for 7 minutes and 30 seconds in an air atmosphere, the sheet resistance increase rate was within 20%,
Visible light transmittance _Tv is 78% or more,
The haze rate is 15% or more,
The shielding coefficient SC is 0.90 or less.

Therefore, the third glass member 300 can obtain the same effects as those of the first glass member 100 and the second glass member 200 described above. That is, when the 3rd glass member 300 is applied to a glass house, the heat-shielding fall by high temperature can be suppressed significantly. In addition, it is possible to incorporate enough sunlight into the glass house, and the good light diffusibility significantly suppresses the above-mentioned “shade” problem and significantly reduces the running cost of the glass house. The effect that can be obtained.

(Fourth configuration)
In FIG. 4, the cross section of another glass member by one Embodiment of this invention is shown typically.

As shown in FIG. 4, still another glass member (hereinafter referred to as “fourth glass member”) 400 according to an embodiment of the present invention is disposed on a glass substrate 410 and on both sides of the glass substrate 410. Each layer.

More specifically, the glass substrate 410 has a first surface 412 and a second surface 414. The first surface 412 has a first undercoat layer 450 and a first surface in the order closer to the glass substrate 410. Two undercoat layers 420 and a heat shielding layer 430 are disposed. On the other hand, an antifouling layer 480 is disposed on the second surface 414 of the glass substrate 410.

The fourth glass member 400 has a first side 402 and a second side 404, the first side 402 corresponds to the side of the thermal barrier layer 430, and the second side 404 is an antifouling layer. This corresponds to the 480 side.

Here, the first surface 412 of the glass substrate 410 has a relatively rough surface. For example, the first surface 412 may have an arithmetic average roughness Ra in the range of 50 μm to 1500 μm. For example, the glass substrate 410 may be made of template glass.

Further, the glass substrate 110 is made of, for example, highly transmissive glass in which the content of iron components is suppressed. The thickness of the glass substrate 110 is, for example, in the range of 1.5 mm to 6 mm. The thickness is preferably in the range of 2 mm to 5 mm.

On the other hand, the first undercoat layer 450 may have the same configuration as the first undercoat layer 350 in the third glass member 300 described above. Further, the second undercoat layer 420 may have the same configuration as the second undercoat layer 320 in the third glass member 300 described above.

The first undercoat layer 450 has a thickness of 3 nm to 20 nm, for example. The thickness is preferably in the range of 5 nm to 15 nm. Further, the second undercoat layer 420 has a thickness of 10 nm to 60 nm, for example. The thickness is preferably in the range of 15 nm to 50 nm, and more preferably in the range of 20 nm to 45 nm.

Moreover, the heat shield layer 430 may have the same configuration as the heat shield layer 130 in the first glass member 100 described above.

The heat shield layer 430 has a thickness of 100 nm to 1000 nm, for example. The thickness is preferably in the range of 120 nm to 800 nm, more preferably in the range of 140 nm to 700 nm, and still more preferably in the range of 150 nm to 500 nm.

The antifouling layer 480 may have the same configuration as the antifouling layer 180 of the first glass member 100. Further, the antifouling layer 480 may be omitted.

The fourth glass member 400 also has the same characteristics as the first glass member 100 to the third glass member 300 described above. That is, the fourth glass member 400 is
When the sample cut into 10 mm square was heat-treated at 670 ° C. for 7 minutes and 30 seconds in an air atmosphere, the sheet resistance increase rate was within 20%,
Visible light transmittance _Tv is 78% or more,
The haze rate is 10% or more,
The shielding coefficient SC is 0.90 or less.

Therefore, also in the fourth glass member 400, the same effect as that of the first glass member 100 described above can be obtained. That is, when the 4th glass member 400 is applied to a glass house, the heat-shielding fall by high temperature can be suppressed significantly. In addition, it is possible to incorporate enough sunlight into the glass house, and the good light diffusibility significantly suppresses the above-mentioned “shade” problem and significantly reduces the running cost of the glass house. The effect that can be obtained.

(Manufacturing method of the glass member by one Embodiment of this invention)
Next, with reference to FIG. 5, an example of the manufacturing method of the glass member by one Embodiment of this invention which has the above characteristics is demonstrated. Here, as an example, the manufacturing method will be described by taking the second glass member 200 shown in FIG. 2 as an example.

FIG. 5 schematically shows an example of a flow of a method for manufacturing the second glass member 200 (hereinafter referred to as “first manufacturing method”).

As shown in FIG. 5, the first manufacturing method is:
(A) installing an undercoat layer on the first surface of the glass substrate (step S110);
(B) On the undercoat layer, a step of installing a first heat shield layer and a second heat shield layer in order (step S120);
(C) installing an antifouling layer on the second surface of the glass substrate (step S130);
Have

Hereafter, each step will be described in detail. In the following description, the reference numerals shown in FIG. 2 are used for representing each member for the sake of clarity.

(Step S110)
First, the glass substrate 210 is prepared.

As described above, the type of glass substrate 210 is not particularly limited, a glass substrate 210, using a high transmittance glass Fe component is suppressed, it is possible to increase the visible light transmittance T _v. For example, the glass substrate 210 is a soda lime silicate high transmission glass.

Next, the undercoat layer 220 is disposed on the first surface 212 of the glass substrate.

The undercoat layer 220 can be formed using various film forming methods such as a chemical vapor deposition (CVD) method, an electron beam vapor deposition method, a vacuum deposition method, a sputtering method, and a spray method.

For example, when the undercoat layer 220 is composed of a silicon oxide layer (SiO ₂ ), the undercoat layer 220 may be formed by an atmospheric pressure CVD method. In this case, gaseous raw materials such as monosilane, tetraethoxysilane, oxygen, carbon dioxide, and nitrogen can be used as the raw material. The source gas may be mixed on the substrate before being conveyed onto the first surface 212 of the glass substrate 210. Alternatively, the source gas may be mixed on the first surface 212 of the glass substrate 210.

Further, for example, when the undercoat layer 220 is composed of a silicon oxycarbide layer (SiOC), when the undercoat layer 220 is formed by an atmospheric pressure CVD method, methane, ethylene, and / or acetylene is used as a source gas. The carbon-containing gas may be contained. When such a carbon-containing gas is used, it becomes easy to form a particulate silicon compound together with the film-like silicon compound, and the haze ratio can be increased.

The temperature of the glass substrate 210 when forming the undercoat layer 220 is preferably 700 ° C. to 1100 ° C. When the temperature of the glass substrate 210 is lower than 700 ° C. or higher than 1100 ° C., the film formation rate tends to decrease.

(Step S120)
Next, the first heat shield layer 230 and the second heat shield layer 240 are sequentially formed on the undercoat layer 220.

The thermal barrier layer 230 can be formed by using various film forming methods such as a chemical vapor deposition (CVD) method, an electron beam vapor deposition method, a vacuum deposition method, a sputtering method, and a spray method.

For example, when the first heat shield layer 230 is formed of a tin oxide layer (SnO ₂ ), the first heat shield layer 230 may be formed by an atmospheric pressure CVD method. In this case, an inorganic tin compound such as tin tetrachloride or an organic tin compound can be used as a raw material.

Here, the organic tin compound means a tin compound containing an organic group, in which the organic group and a tin atom are bonded by a bond between a carbon atom and a tin atom. In particular, the organic group is preferably a hydrocarbon group such as an alkyl group and an alkenyl group.

Two or more organic groups may be bonded to the tin atom. As the organic group, an alkyl group having 1 to 10 carbon atoms is preferable. As the reactive group and atom bonded to the tin atom other than the organic group, a chlorine atom is preferable. The organic tin compound is preferably a tetravalent tin compound, that is, a tin (IV) compound. Examples of the organic tin compound include monomethyltin trichloride, dimethyltin dichloride, monobutyltin trichloride, tetramethyltin, tetrabutyltin, and dibutyltin dichloride. Among these, monobutyltin trichloride (hereinafter referred to as MBTC) is preferable because it is easily available, inexpensive, and easy to handle.

Next, the second heat shield layer 240 is formed.

The second thermal barrier layer 240 can be formed using various film forming methods such as a chemical vapor deposition (CVD) method, an electron beam vapor deposition method, a vacuum deposition method, a sputtering method, and a spray method. it can.

For example, when the second heat shield layer 240 is formed of a fluorine-doped tin oxide layer (SnO ₂ ), the second heat shield layer 240 may be formed by an atmospheric pressure CVD method. In this case, as a raw material, a mixture of an inorganic or organic tin compound used in the film formation of the first heat shield layer 230 and a fluorine compound is used.

Fluorine compounds include hydrogen fluoride and trifluoroacetic acid. As the fluorine compound, hydrogen fluoride is particularly preferable.

In any film formation of the first heat-insulating layer 230 and the second heat-insulating layer 240, the source gas may be transported after being mixed in advance. Alternatively, the source gas may be mixed on the surface of the film formation target. When the raw material is a liquid, the raw material may be vaporized using a bubbling method or a vaporizer.

The amount of water relative to 1 mol of tin compound in the raw material gas is preferably 10 to 30 mol. If the amount of water is less than 10 mol, the resistance value of the film to be formed tends to increase, and as a result, the shielding coefficient SC tends to increase. Further, light absorption tends to increase.

On the other hand, if the amount of water is more than 30 mol, as the amount of water increases, the raw material gas capacity increases and the flow rate of the raw material gas increases, so that the film deposition efficiency may be reduced. The amount of water relative to 1 mol of the tin compound is more preferably 15 to 25 mol, and further preferably 18 to 22 mol.

When the source gas contains oxygen, the amount of oxygen with respect to 1 mol of the tin compound in the source gas is preferably more than 0 to 20 mol, and more preferably 4 to 20 mol. If the amount of oxygen is less than 4 mol, the resistance value and light absorption of the film to be produced may increase. On the other hand, when the amount of oxygen exceeds 20 mol, the raw material gas capacity increases, and the flow rate of the raw material gas increases, so that the film deposition efficiency may be lowered. The amount of oxygen relative to 1 mol of the tin compound is more preferably 6 to 15 mol, and further preferably 8 to 10 mol.

In the formation of the second heat shielding layer 240, the amount of the fluorine compound relative to 1 mol of the tin compound in the raw material gas is preferably 0.2 to 1.2 mol. When the amount of the fluorine compound is less than 0.2 mol or more than 1.2 mol, the resistance value of the formed film tends to increase. The amount of the fluorine compound relative to 1 mol of the tin compound is more preferably 0.4 to 1.0 mol, and further preferably 0.5 to 0.7 mol.

The temperature of the glass substrate 210 when forming the first heat shield layer 230 and the second heat shield layer 240 is preferably 500 ° C. to 650 ° C. When the temperature of the glass is lower than 500 ° C., the formation rate of the first and second

heat shielding layers

230 and 240 is lowered, and the crystallinity is lowered. As a result, a decrease in haze rate and a decrease in mobility occur (a decrease in mobility corresponds to an increase in sheet resistance, and an increase in sheet resistance corresponds to a decrease in heat shielding properties). On the other hand, when the temperature of the glass substrate 210 is higher than 650 ° C., film formation is performed with the glass having a low viscosity, and thus there is a risk of warping in the process of lowering the glass to room temperature.

The temperature of the glass substrate 210 is preferably 520 ° C. to 750 ° C., more preferably 540 ° C. to 700 ° C.

In addition, the formation of the coating on the glass substrate in step S110 and step S120 may be performed by an on-line method in the process of producing the glass with the float facility, or the glass obtained by the float method is reheated. An off-line method for carrying out the film may be used.

(Step S130)
Next, the antifouling layer 280 is provided on the second surface 214 of the glass substrate 210.

The antifouling layer 280 can be formed using various film forming methods such as a chemical vapor deposition (CVD) method, an electron beam vapor deposition method, a vacuum deposition method, a sputtering method, and a spray method.

The example of the manufacturing method has been described above by taking the second glass member 200 as an example.

However, the manufacturing method described is merely an example, and the second glass member 200 may be manufactured by other manufacturing methods.

For example, in the above-described example, the antifouling layer 280 is formed after each layer on the first surface 212 of the glass substrate 210 is formed in step S130. However, first, the antifouling layer 280 may be formed on the second surface 214 of the glass substrate 210 and then the layers 220 to 240 may be installed on the first surface 212 of the glass substrate 210.

In addition, the first manufacturing method may further include a step (strengthening step) of strengthening the glass substrate 210 by air cooling or chemical strengthening. This strengthening process may be performed in any order, for example, before step S110 or after step S130.

The strength of the glass substrate 210 and further the second glass member 200 is improved by performing the strengthening step. When the glass member is subjected to a tempering treatment after film formation, chemical tempering may cause warping of the glass member as a result of different ion exchange methods on the front and back surfaces, and thus treatment by air cooling tempering is preferred.

In addition, the formation of the coating on the glass substrate in step S130 may be performed by an on-line method in the process of producing the glass with the float facility, or the film obtained by the float method is reheated to form the film. It may be by offline method.

It will be apparent to those skilled in the art that other various modifications are possible.

Moreover, it is easy for those skilled in the art that the 1st glass member 100, the 3rd glass member 300, and the 4th glass member 400 can be manufactured by changing a part of above-mentioned 1st manufacturing method. Can be estimated.

Next, examples of the present invention will be described. In the following description, Examples 1 to 6, Example 8 and Example 10 are examples, and Examples 7 and 9 are comparative examples.

(Example 1)
A glass member having the configuration as shown in FIG. 1 was configured.

The glass substrate used was a highly transparent soda lime silicate glass with a thickness of 4 mm.

An SiOC film was formed as an undercoat layer on one surface (first surface) of this glass substrate. The SiOC layer was formed by the CVD method (target film thickness 85 nm). The surface of the undercoat layer was adjusted to have a surface roughness (arithmetic average roughness Ra) of 10 nm to 100 nm.

Next, a fluorine-doped SnO ₂ layer was formed as a heat shield layer on the SiOC layer. The fluorine-doped SnO ₂ layer was formed by the CVD method using MBTC and hydrogen fluoride as raw materials (target film thickness 340 nm). The fluorine doping amount was 0.5 to 0.7 as the molar ratio of the tin compound to the fluorine compound.

In addition, the antifouling layer was not installed on the second surface of the glass substrate.

The obtained glass member is referred to as “glass member according to Example 1”.

(Example 2)
A glass member was constructed in the same manner as in Example 1.

However, in Example 2, soda lime glass having a thickness of 3 mm was used as the glass substrate. The surface of the undercoat layer was made to have a surface roughness (arithmetic average roughness Ra) in the range of 10 nm to 100 nm.

Other conditions are the same as in Example 1.

The obtained glass member is referred to as “glass member according to Example 2”.

(Example 3)
A glass member was constructed in the same manner as in Example 2.

However, in Example 3, soda lime glass having a thickness of 4 mm was used as the glass substrate. In addition, the thickness of the first heat shield layer was set to 190 nm.

Other conditions are the same as in Example 2.

The obtained glass member is referred to as “glass member according to Example 3”.

(Example 4)
A glass member having the structure as shown in FIG.

An SiOC film was formed as an undercoat layer on one surface (first surface) of this glass substrate. The SiOC layer was formed by the CVD method (target film thickness 85 nm).

Next, an undoped SnO ₂ film was formed on the SiOC layer as a first heat shield layer. The SnO ₂ layer was formed by a CVD method using MBTC as a raw material (target film thickness 170 nm). Further, a fluorine-doped SnO ₂ layer was formed as a second heat shield layer on the first heat shield layer. The fluorine-doped SnO ₂ layer was formed by CVD using MBTC and hydrogen fluoride as raw materials (target film thickness 170 nm). The fluorine doping amount was 0.5 to 0.7.

The obtained glass member is referred to as “glass member according to Example 4”.

(Example 5)
A glass member having the structure as shown in FIG. 3 was constructed.

A TiO ₂ layer was formed as a first undercoat layer on one surface (first surface) of the glass substrate. The TiO ₂ layer was formed by the CVD method (target film thickness 10 nm). Next, a SiO ₂ layer was formed as a _second undercoat layer on the first undercoat layer. The SiO ₂ layer was formed by the CVD method (target film thickness 35 nm).

Next, a fluorine-doped SnO ₂ layer was formed as a first heat shielding layer on the SiO ₂ layer. The first thermal barrier layer was formed by CVD using hydrogen fluoride and SnCl ₄ as raw materials (target film thickness 170 nm). The fluorine doping amount was 0.5 to 0.7.

Further, a fluorine-doped SnO ₂ layer was formed as a second heat shield layer on the first heat shield layer. The second thermal barrier layer was formed by the CVD method using MBTC and hydrogen fluoride as raw materials (target film thickness 170 nm). The fluorine doping amount was 0.5 to 0.7.

The obtained glass member is referred to as “glass member according to Example 5”.

(Example 6)
A glass member having the structure as shown in FIG. 4 was constructed.

For the glass substrate, a template glass (soda lime silicate glass) having a thickness of 4 mm was used. One surface of the glass substrate has a surface roughness with an arithmetic average roughness Ra in the range of 50 μm to 1500 μm.

A TiO ₂ layer was formed as a first undercoat layer on the first surface of the glass substrate. The TiO ₂ layer was formed by the CVD method (target film thickness 10 nm). Next, a SiO ₂ layer was formed as a _second undercoat layer on the first undercoat layer. The SiO ₂ layer was formed by the CVD method (target film thickness 35 nm).

Next, a fluorine-doped SnO ₂ layer was formed as a heat shield layer on the SiO ₂ layer. The thermal barrier layer was formed by the CVD method using MBTC and hydrogen fluoride as raw materials (target film thickness 350 nm). The fluorine doping amount was 0.5 to 0.7.

The obtained glass member is referred to as “glass member according to Example 6”.

(Example 7)
A glass member was formed by the same method as in Example 2 described above.

However, in Example 7, soda lime glass having a thickness of 4 mm was used as the glass substrate. The thickness of the heat shield layer was 490 nm.

Other conditions are the same as in Example 2.

The obtained glass member is referred to as “glass member according to Example 7.”

(Example 8)
A glass member was formed by the same method as in Example 2 described above.

However, in Example 8, soda lime glass having a thickness of 5 mm was used as the glass substrate. The thickness of the heat shield layer was 340 nm.

Other conditions are the same as in Example 2.

The obtained glass member is referred to as “glass member according to Example 8”.

(Example 9)
The soda lime glass substrate having a thickness of 4 mm used in Example 3 was used as the glass member according to Example 9. That is, the glass member according to Example 9 is composed only of a glass substrate and does not have any coating.

(Example 10)
The glass member was manufactured by the following method.

Next, a fluorine-doped SnO ₂ layer was formed as a first heat shielding layer on the SiO ₂ layer. The first thermal barrier layer was formed by CVD using hydrogen fluoride and SnCl ₄ as raw materials (target film thickness 350 nm). The fluorine doping amount was 0.5 to 0.7.

The obtained glass member is referred to as “glass member according to Example 10”.

Table 1 below summarizes the configuration of each glass member.

(Evaluation)
The following evaluation was performed using each glass member described above.

(Shielding coefficient SC)
As described above, the shielding coefficient SC is expressed by the following equation (1) when the solar heat gain rate measured in accordance with ISO 9050: 2003 is a g value (%):

SC = g value / 0.88 (1) Formula
Here, the g value was calculated from the measurement with a spectrophotometer (LAMBDA950 manufactured by PerkinElmer).

(Visible light transmittance T _v )
Visible light transmittance _{T v,} as described above, ISO9050: conforms to 2003, calculated from the spectrophotometric measurements (Perkin Elmer LAMBDA950).

(Haze rate)
The haze ratio of each glass member was measured using a haze meter (HZ-2 manufactured by Suga Test Instruments).

(Sheet resistance increase rate)
As described above, the sheet resistance increase rate is expressed by (sheet resistance of the sample after heat treatment−sheet resistance of the sample before heat treatment) / (sheet resistance of the sample before heat treatment) × 100.

The heat treatment was performed using a sample cut into a 10 mm square from each glass member. The heat treatment was carried out by holding each sample at 670 ° C. for 7 minutes and 30 seconds in an air atmosphere.

For measurement of sheet resistance, Loresta MCP-T360 manufactured by Mitsubishi Chemical Analytech was used.

Table 2 summarizes the evaluation results obtained for each glass member.

From the evaluation results obtained, it was found that the glass members according to Examples 1 to 6 and Example 8 each had an SC value of 0.9 or less, and had good heat shielding properties. Further, in the glass members according to Examples 1 to 6 and Example 8, the visible light transmittance _Tv was 78% or more, and it was found that the glass members had good transmittance. In addition, the glass members according to Examples 1 to 6 and Example 8 all had a haze ratio of 10% or more, and were found to have good light diffusibility. Furthermore, in the glass members according to Examples 1 to 6, Example 8, and Example 10, the sheet resistance increase rate was 20% or less, and it was found that the glass members had good heat resistance.

In contrast, in the glass members according to Examples 7 and 9, at least one of the SC value, visible light transmittance, haze rate, and sheet resistance increase rate did not satisfy the predetermined value. From this, it can be said that the glass members according to Examples 7 and 9 have less applicability to the glass house than the glass members according to Examples 1 to 6 and Example 8.

This application claims priority based on Japanese Patent Application No. 2016-000238 filed on January 4, 2016, the entire contents of which are incorporated herein by reference.

100

First glass member

102, 202, 302, 402

First side

104, 204, 304, 404

Second side

108, 208, 308, 408

Light

110, 210, 310, 410

Glass substrate

112, 212, 312 412

First surface

114, 214, 314, 414

Second surface

120, 220 Undercoat layer 130

Thermal barrier layer

180, 280, 380, 480 Antifouling layer 200

Second glass member

230, 330, 430 First

Thermal barrier layer

240, 340, 440 Second thermal barrier layer 300

Third glass member

320, 420

Second undercoat layer

350, 450 First undercoat layer 400 Fourth glass member 480 Antifouling layer

Claims

A glass member having a glass substrate,
The glass substrate has a first surface and a second surface;
A coating is placed on the first surface of the glass substrate,
The coating is from the side close to the glass substrate,
An undercoat layer containing silicon oxide;
A thermal barrier layer containing tin oxide;
Have
When the sample cut into a 10 mm square is heat-treated at 670 ° C. for 7 minutes and 30 seconds in an air atmosphere, the sheet resistance increase rate is within 20%.
When the glass member is measured from the glass substrate side,
ISO9050: measured according to 2003 the visible light transmittance T v is not less 78% or more,
The haze rate is 10% or more,
When the solar heat acquisition rate measured according to ISO 9050: 2003 is g value (%), and the value represented by the following formula (1) is the shielding coefficient SC,

SC = g value / 0.88 (1) Formula
The glass member whose SC is 0.90 or less.
The glass member according to claim 1, wherein the heat shielding layer includes tin oxide doped with fluorine and / or antimony.
The thermal barrier layer is composed of two layers, a first layer and a second layer, from the side close to the glass substrate,
The glass member according to claim 1, wherein the first layer includes undoped tin oxide, and the second layer includes tin oxide doped with fluorine and / or antimony.
The thermal barrier layer is composed of two layers, a first layer and a second layer, from the side close to the glass substrate,
Both the first layer and the second layer include tin oxide doped with fluorine and / or antimony,
The glass member according to claim 1, wherein the second layer has a higher carrier concentration than the first layer.
The glass member according to claim 1 or 2, wherein the arithmetic surface roughness Ra on the surface of the undercoat layer is in the range of 1 nm to 150 nm.
The glass member according to claim 1 or 2, wherein the first surface of the glass substrate has a surface roughness Ra in the range of 50 袖 m to 1500 袖 m.
The undercoat layer is composed of two layers, a bottom layer and an upper layer, from the side close to the glass substrate,
The glass member according to claim 1, 2, 4, or 6, wherein the bottom layer includes titanium oxide, and the top layer includes silicon oxide.
The glass member according to any one of claims 1 to 7, wherein an antifouling layer is provided on the second surface of the glass substrate.
The glass member according to any one of claims 1 to 8, wherein the glass substrate is made of highly transmissive glass.