JPH10152345A - Heat ray-shielding glass and heat ray-shielding multiple glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain heat ray-shielding glass capable of being also used as a glass single plate and improved in thermal and optical characteristics by forming a conductive coating film on the surface of a glass plate comprising a glass composition which comprises a specific basic glass composition, a coloring component containing all iron oxides and FeO in a desired amount based on the whole iron oxides. SOLUTION: This heat ray-shielding glass is obtained by forming a conductive coating film comprising oxides on the surface of a glass plate comprising a glass composition which comprises a basic glass composition comprising 65-80wt.% of SiO2 , 0-5wt.% of Al2 O3 , 0-5wt.% of B2 O3 , 0-10wt.% of MgO, 5-15wt.% of CaO, 10-18wt.% of NaO, 0-5wt.% of K2 O, 5-15wt.% of MgO+CaO, and 10-20wt.% of Na2 O+K2 O, a coloring component containing all iron oxides in an amount of 0.46-1.50wt.% (in terms of Fe2 O3 ), and FeO in an amount of 22-56wt.% (in terms of Fe2 O3 ). Namely the heat ray-shielding glass is obtained by forming a conductive coating film 2 on the surface of the glass plate 1 by a thermal decomposition method using a tin raw material, an indium raw material, a zinc raw material, a chlorine, a fluorine raw material, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-shielding glass for suppressing inflow of solar energy, and more particularly to a double-glazing using the heat-shielding glass.

[0002]

2. Description of the Related Art For the purpose of, for example, reducing the cooling load, a heat ray reflective glass in which a heat ray reflective coating is formed on the surface of a glass plate or a heat ray absorbing glass in which a trace component is added to a glass plate have been used. As the heat ray reflection glass, those having a heat ray reflection film made of a multilayer film including a film made of titanium oxide and a titanium nitride film have been put into practical use.As the heat ray absorption glass, a metal compound such as cobalt, nickel, and selenium has been used as a trace component. Has been put to practical use.

Further, as a heat ray shielding glass utilizing the reflection characteristics of the conductive film in the near infrared region, a glass plate having a multilayer film including a metal layer is formed so that the multilayer film faces the air layer side. Double glazing is known. Examples of this type of double glazing include, for example, Japanese Patent Application Laid-Open No. 7-10609.
In Japanese Patent Application Laid-Open No. H10-157, there is disclosed a double-layer glass in which a glass in which a multilayer film including a silver layer is formed on the surface of heat ray absorbing glass is arranged such that the multilayer film is on the air layer side.

[0004]

However, the double glazing disclosed in Japanese Patent Application Laid-Open No. 7-10609 is to obtain a heat ray shielding property effectively by combining a heat ray absorbing glass and a conductive film. Since a multilayer film including a silver layer is used, coating durability is not sufficient. The present invention
It is an object of the present invention to provide a heat ray shielding glass that can be used as a single veneer glass and that has excellent thermal and optical properties.

[0005]

In order to achieve the above object, the heat ray shielding glass according to claim 1 is essentially 65 to 80% SiO ₂ , expressed in% by weight, and 0 to 5%. A
l ₂ O _3, 0~5% of B ₂ O _3, 0~10% of MgO,. 5 to
15% of CaO, 10 to 18 percent of Na ₂ O, 0 to 5% of the K ₂ O, 5 to 15 percent of MgO + CaO and 10-20
% Na ₂ O + K ₂ O;
Consists of a coloring component comprising total iron oxide in terms of 6-1.50% Fe ₂ O _3, and, FeO which in terms of Fe ₂ O ₃ is made of a glass composition is from 22 to 56% of the total iron oxide It is characterized in that a conductive coating consisting essentially of an oxide is formed on the surface of a glass plate.

The heat ray shielding glass according to the first aspect effectively shields heat rays from the outdoor side by using the conductive coating as the indoor side. In such a usage mode, solar radiation is effectively blocked by the heat ray absorbing effect of the coloring component contained in the glass plate and the heat ray reflecting effect of the conductive coating formed on the surface of the glass plate. That is, the conductive coating reflects the heat rays absorbed and re-emitted by the glass plate and the heat rays which are not absorbed by the glass plate and flow into the room, thereby suppressing the inflow of solar radiation into the room. On the other hand, since this conductive film is essentially composed of an oxide and has superior durability compared to a conductive film containing a metal layer such as a silver layer, it is not necessary to form a double-glazed glass sheet. Can be used with

Certainly, in terms of performance such as vertical emissivity, a conductive film composed of a multilayer film including a silver layer is generally superior to a conductive film composed of an oxide. In view of this, in the heat ray shielding glass according to the first aspect, in consideration of the combination with the conductive coating made of oxide, the ratio of FeO to the total iron oxide including the predetermined iron oxide is set to a predetermined range. A heat-shielding property is to be ensured by using a glass plate containing components.

According to the heat ray shielding glass of the first aspect, the coloring component absorbs not only heat rays but also ultraviolet rays. That is, among the iron oxides contained in the glass plate,
FeO mainly enhances infrared absorption performance, and Fe ₂ O ₃ mainly plays a role in enhancing ultraviolet absorption performance. When the total iron oxide content is less than 0.46% by weight in terms of Fe ₂ O ₃ , these properties are not sufficiently exhibited, while when it exceeds 1.50% by weight, the visible light transmittance is excessively lowered. According to the double glazing of claim 1, the amount of FeO is 22 to 5 of the total iron oxide.
6% is set so as to obtain preferable values for both the performance and the visible light transmittance.

The coloring component of the glass plate is TiO.
₂ , other minor components such as CeO ₂ , CoO, Cr ₂ O ₃ and V ₂ O ₅ may be contained.

[0010] Of these trace components, TiO ₂ is an ultraviolet absorbing component, but it has an effect of absorbing visible light and reducing the visible light reflectance, so that it is preferably added as a coloring component. However, if the TiO ₂ content exceeds 1.0% by weight, the absorption on the short wavelength side of the visible light becomes too large. Therefore, in the present invention, it is more preferable to add 0 to 1.0% by weight. CeO ₂ is an ultraviolet absorbing component, and may be added as a coloring component in an amount of 0 to 2.0% by weight.
V ₂ O _{5 is} also an ultraviolet absorbing component,
2.0% by weight may be added. CoO may be added in an amount of 0 to 2.0% by weight for the purpose of adjusting the visible light transmittance.

Further, other oxides may be added to the above-mentioned glass plate as long as the object of the present invention is not impaired.
For example, at least one of ZnO, MnO, SnO _2, and MoO ₃ is 0 to 1.0% by weight in total, S in terms of SO ₃ is 0 to 1.0% by weight, color tone adjustment, reduction degree adjustment, and the like. It may be added for the purpose of.

Preferred glass compositions for constituting the above-mentioned glass sheet are exemplified below (the percentages in the following examples are also% by weight). The above base glass component and 0.46 to 1.50% F
It is composed of total iron oxide in terms of e ₂ O ₃ and a coloring component containing 0.1 to 1.0% of TiO ₂ , and FeO in terms of Fe ₂ O ₃ is 22 to 56% of the total iron oxide. Is a glass. The above base glass component and 0.46 to 1.50% F
Total iron oxide converted to e ₂ O ₃ and 0 to 1.0% Ti
Consists of a coloring component comprising O _2, and glass FeO in terms of Fe ₂ O ₃ is 36 to 56% of the total iron oxide. The above base glass component and 0.46-1.00% F
It is composed of total iron oxide in terms of e ₂ O ₃ and a coloring component containing 0.1 to 1.0% of TiO ₂ , and FeO in terms of Fe ₂ O ₃ is 36 to 56% of the total iron oxide. Is a glass. The above base glass component and 1.00 to 1.50% of F
Total iron oxide converted to e ₂ O ₃ and 0 to 1.0% Ti
Consists of a coloring component comprising O _2, and glass FeO in terms of Fe ₂ O ₃ is 22 to 56% of the total iron oxide. The above base glass component and 1.00 to 1.50% of F
Total iron oxide converted to e ₂ O ₃ and 0 to 1.0% Ti
Consists of a coloring component comprising O _2, and glass FeO in terms of Fe ₂ O ₃ is 36 to 56% of the total iron oxide.

In the above glass components, S is S
Converted to O ₃ , and for each, 0.05
0.18% by weight, and about 0.05-
It is preferable to add in the range of 0.25% by weight.

The optical characteristics of these glasses are as follows: 3 mm thick glass having a solar transmittance of less than 55%;
The dominant wavelength measured using a glass C light source also converted to a thickness of 3 mm is 498 to 525 nm, and the stimulation purity measured using a glass C light source also converted to a thickness of 3 mm is 6%.
It is preferably less than.

Similarly, for the 3 mm thickness, the solar transmittance of the glass is less than 45%, and the dominant wavelength measured using the glass C light source also converted to the 3 mm thickness is 498 to 525 nm, and the 3 mm thickness is also 3 mm. It is preferable that the stimulus purity measured using the converted glass C light source is less than 6%.

The reasons for limiting the basic glass composition of the above-mentioned glass sheet are as follows. SiO ₂ is a main component forming the skeleton of the glass. If it is less than 65% by weight, the durability decreases, and if it exceeds 80% by weight, it becomes difficult to melt the glass. Al ₂ O ₃ is a component that improves the durability of the glass, but if it exceeds 5% by weight, it becomes difficult to melt the glass. B
₂ O ₃ is used for improving the durability of the glass and as a melting aid. However, if it exceeds 5% by weight, it will be difficult to form a glass plate due to volatilization of this component. MgO and CaO are used to improve the durability of the glass and to adjust the devitrification temperature and viscosity during molding.
Or CaO is less than 5% by weight or 15% by weight.
If the content exceeds% by weight, the devitrification temperature increases. MgO and CaO
Is less than 5% by weight, the durability of the glass decreases. Na ₂ O and K ₂ O are used as glass melting accelerators. If the total amount of Na ₂ O and K ₂ O is less than 10% by weight, the effect of accelerating the melting cannot be obtained, while the total amount is 20% by weight.
If it exceeds, the durability of the glass decreases.

The heat ray shielding glass according to the second aspect is the heat ray shielding glass according to the first aspect, wherein the conductive coating is:
The electron concentration is 1 × 10 ²⁰ to 2 × 10 ²¹ cm ^-3 , the electron mobility is 5 to 50 cm ² / V · s, and the film thickness is 5 to 1
000 nm. This conductive film conforms to Drude's free electron theory.

The conductive film according to the second aspect has excellent reflection characteristics in the near-infrared region. Therefore, by forming this film, a heat ray shielding glass excellent in heat ray shielding properties can be obtained. Examples of such a conductive film include the following. a) A coating consisting essentially of tin oxide to which a trace component (for example, one or more of fluorine, chlorine, antimony, etc.) is added. b) a coating consisting essentially of indium oxide or of tin-containing indium oxide. c) A coating consisting essentially of zinc oxide with added minor components (eg, aluminum).

However, the present invention is not limited to these, and a film obtained by mixing the above a) to c), MgIn ₂ O ₄ , CdGa ₂
A film made of O ₄ or the like, a protective film on any of these films,
A film in which a base film is additionally formed may be used.

If the electron concentration or the electron mobility is lower than the above range, the reflection characteristics of the coating may not be sufficient. On the other hand, considering the balance between the visible light transmittance and the coating durability, it is not necessary to have the electron concentration or the electron mobility to an extent exceeding the above range. For example, when the electron concentration is higher than the above range, the absorption becomes on the long wavelength side in the visible light range, and the visible light transmittance is reduced. When the electron concentration and the electron concentration are in the above range, the film thickness is suitably from 5 to 1000 nm.
-650 nm is preferable, and 250-650 nm is more preferable. On the other hand, the electron concentration is 2.5 × 10 ²⁰
８8.0 × 10 ²⁰ cm ^−3, but the electron mobility is 1
It is preferably from 3 to 40 cm ² / V · s. The electron concentration and the electron mobility can be adjusted by changing the amount of each trace component in the coating.

In the heat-shielding glass according to the second aspect, for example, when the thickness of the glass plate is 3 mm, the solar shading coefficient (measured value from the glass surface on the side opposite to the surface on which the film is formed) is set to 0. 69 or less,
By appropriately selecting the preferred range, the solar shading coefficient when the glass plate thickness is 3 mm is 0.60 or less,
Furthermore, it can be set to 0.50 or less. The solar shading coefficient in this specification refers to a relative value of the solar heat gain when the solar heat gain of a float glass plate having a thickness of 3 mm is set to 0.88. On the other hand, in the heat ray shielding glass according to the second aspect, when the glass plate has a thickness of 3 mm as described above, the visible light transmittance can be 55% or more, and if necessary, 60% or more.

The heat ray shielding glass according to claim 3 is characterized in that the conductive coating is formed on the surface of a glass ribbon manufactured by a float method by a thermal decomposition method. Claim 3
According to the heat ray shielding glass described in the above, on the line by the float method, because the film is formed using the residual heat of the glass melting,
The solar control glass can be manufactured very efficiently. In addition, the durability of the coating is also excellent as compared with a sputtering method or the like. Here, as the thermal decomposition method, a chemical vapor method (CVD method) can be used in addition to a spray method such as a solution spray method, a dispersion liquid spray method, and a powder spray method. Note that it is preferable to perform the chemical vapor deposition method in a high-temperature float bath because a uniform coating can be obtained.

The heat ray shielding glass according to any one of the first to third aspects can be used as a single glass plate. However, in order to further enhance the heat ray shielding property and to improve the heat transmission coefficient, the heat ray shielding glass according to the fourth aspect is required. As described, it can also be used as a double glazing. That is, a heat ray shielding multilayer glass comprising the heat ray shielding glass according to any one of claims 1 to 3, wherein the heat ray shielding glass has a surface on which a conductive coating is formed as an air layer side. When used as a layered glass, it is possible to obtain a glass member having more excellent heat insulating properties. It is preferable to use the heat ray shielding glass according to any one of claims 1 to 3 as an outdoor side of the double-layer glass.
In this case, the glass plate on the indoor side is not particularly limited, but typically, a colorless and transparent float glass plate having a trace component is used. In addition, it is preferable that the width of the air layer of the multi-layer glass is 6 mm or more.

[0024]

FIG. 1 is a schematic sectional view of a heat ray shielding glass according to the present invention, in which a conductive film 2 is formed on a surface of a glass plate 1 containing a predetermined coloring component. . FIG. 2 is a schematic cross-sectional view when the heat ray shielding glass according to the present invention is used as a double glazing. The first glass plate 3 on which the conductive coating 4 is formed and the second glass plate 5 are spaced apart from each other in a plane direction so as to form an air layer 6. Are adhered by a sealant 7. Spacers 8 having a desiccant therein are arranged between the peripheral edges of the glass plate to stably hold the glass plate and keep the air in the air layer 6 in a dry state. In addition, the spacer 8 and the sealing agent 7 are not particularly limited, and general ones used for ordinary double glazing can be used.

The following can be exemplified as the raw materials that can be used when the conductive films 2 and 4 are formed by the thermal decomposition method. That is, as a tin raw material, tin tetrachloride, tetramethyltin, dibutyltin dichloride, tetrabutyltin, dioctyltin dichloride, dimethyltin dichloride, tetraoctyltin, dibutyltin oxide, dibutyltin dilaurate, dibutyltin fatty acid, monobutyltin fatty acid, Monobutyltin trichloride, dibutyltin diacetate, dioctyltin diacetate, dioctyltin dilaurate, bisacetylacetonatotin, and the like, as indium raw materials, trimethylindium, triethylindium, indium chloride, indium acetylacetonate, trimethylindium diisopropylamine Adduct, triphenylindium, indium trifluoroacetylacetonate, indium hexafluoroacetylacetonate, Le indium chloride, diethyl indium chloride, indium fluoride, indium formate, naphthenic acid indium, diethyl monoethoxy indium, indium tris dibenzoyl meta titanate, indium triisopropoxide. Examples of the zinc starting material, dimethyl zinc, diethyl zinc,
Zinc acetate, zinc acetylacetonate, zinc lactate, and the like. Further, as a chlorine raw material, chlorine, hydrogen chloride, and the like contained in the tin raw material are used. As a fluorine raw material, ammonium fluoride, hydrogen fluoride, and trifluorofluoride are used. Acetic acid, various chlorofluorocarbon gases (for example, 1,1 difluoroethane gas), and the like are used as antimony raw materials. Antimony, antimony oxychloride, etc., and aluminum raw materials include aluminum acetylacetonate. In addition,
As the antimony raw material, a combination of a solvent to which Sb ₂ O ₅ and HCl are added may be used.

[0026]

【Example】

(Examples 1 to 3) Quartz sand, dolomite, limestone, soda ash, potassium carbonate, boron oxide, blister glass, ferric oxide and a carbon-based reducing agent are appropriately mixed so as to obtain a predetermined glass composition, Further, for Examples 1 and 2, titanium oxide was also mixed, and this raw material was heated at 1500 ° C. in an electric furnace. After melting for 4 hours, the glass substrate was poured on a stainless steel plate and cooled to room temperature. The obtained thickness of about 8mm
Was polished to a thickness of 3 mm. The coloring components contained in this glass were as shown in Table 1. The basic glass component of this glass is SiO ₂ :
_{72%, Al 2 O 3:} 1.5%, MgO: 4%, CaO:
_{8%, Na 2 O: 13} %, K 2 O: 0.7% (all% by weight).

After the glass plate was washed and dried, the surface of the glass plate was subjected to chemical vapor deposition using a mixed gas consisting of monobutyltin trichloride, water (steam), oxygen, 1,1-difluoroethane gas and nitrogen. A tin oxide film to which chlorine and fluorine were added was formed by (CVD method). The characteristic values of this glass plate are shown in Table 1. Note that the electron concentration (carrier concentration) and the electron mobility were determined by the Hall effect measurement method by van der Pauw method.

Further, the heat ray shielding glass thus obtained and the colorless float glass having a thickness of 3 mm were arranged apart from each other in the thickness direction, and the desiccant was filled in the peripheral portions of the two glass plates. These were adhered with butyl rubber via an aluminum spacer to be integrated. At this time, the coating surface was set to the air layer side. The thickness of the air layer was 6 mm or 12 mm. Table 2 shows properties of the obtained double-glazed glass.

(Examples 4 and 5) The mixed gas was composed of monobutyltin trichloride, water (steam), oxygen, antimony pentachloride and nitrogen, and the coating was formed of tin oxide to which chlorine and antimony were added. Other than that, the results obtained in the same manner as in the above Examples are also shown in Tables 1 and 2.

(Examples 6 and 7) A glass plate having a thickness of 3 mm obtained in the same manner as in the above example was fixed with a hanging tool.
After holding in an electric furnace set at 650 ° C. for 5 minutes, take out, and spray a raw material solution in which monobutyltin trichloride, water, isopropyl alcohol and ammonium fluoride are dissolved on the surface thereof, and oxidize to which chlorine and fluorine are added. A tin film was formed. The characteristic values obtained for this glass in the same manner as in the above Examples are also shown in Tables 1 and 2.

Example 8 The raw material liquid was monobutyltin trichloride, water, isopropyl alcohol, antimony trichloride and ammonium fluoride.
Tables 1 and 2 also show the results obtained in the same manner as in Examples 6 and 7, except that a tin oxide film to which antimony and fluorine were added was formed.

(Examples 9 to 11) The same procedure as in Examples 1 to 3 was carried out except that the mixed gas was indium acetylacetonate, bisacetylacetonate tin, oxygen and nitrogen, and the coating was an indium oxide film to which tin was added. The results obtained in the same manner are also shown in Tables 1 and 2.

(Examples 12 to 14) A zinc oxide to which aluminum was added was used as a raw material liquid in which aluminum acetylacetonate was suspended in a solution in which zinc acetate was dissolved in water and isopropyl alcohol. Otherwise, Tables 1 and 2 show the results obtained in the same manner as in Examples 6 and 7.
Are shown together.

(Comparative Examples 1 to 4) For comparison, the amount of carbon-based reducing agent was adjusted to change the ratio of FeO to the total iron (Comparative Examples 1 and 2), and the amount of ferric oxide was adjusted. By changing the amount of total iron oxide (Comparative Examples 3 and 4), a film similar to that of Example 2 was formed (Comparative Examples 1 and 3) or a film similar to that of Example 9 was formed (Comparative Example). Examples 2, 4). The properties of these glass plates are also shown in Tables 1 and 2.

[0035]

[Table 1]

[0036]

[Table 2]

From Table 2, it can be seen that the multilayer glasses of Examples 1 to 14 have a solar shading coefficient of 0.59 or less and a visible light transmittance of 50% or more.

[0038]

According to the first aspect of the present invention, there is provided a heat ray shielding glass in which the durability of a coating film is secured so as not to be necessarily used as a double glazing. This heat ray shielding glass is effectively shielded from heat rays by a coloring component contained in the glass plate and a conductive film essentially formed of an oxide formed on the surface of the glass plate. In addition to this effect,
According to the second aspect of the present invention, there is provided a heat ray shielding glass having a low solar radiation shielding coefficient and a low visible light transmittance. Further, according to the third aspect of the present invention, the conductive film is efficiently manufactured. When these glasses are used as a double glazing as described in claim 4, they become a glass window member having more excellent heat insulating properties.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a heat ray shielding glass according to the present invention.

FIG. 2 is a schematic cross-sectional view of the solar control double glass according to the present invention.

[Explanation of symbols]

1: glass plate, 2: 4, conductive coating, 3: first glass plate, 5: second glass plate, 6: air layer, 7: sealant,
8: Spacer

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI C03C 27/06 101 C03C 27/06 101H

Claims (4)

[Claims] 1. Essentially 65 to 80, expressed in% by weight.
% SiO ₂ , 0-5% Al ₂ O ₃ , 0-5% B
₂ O ₃ , 0-10% MgO, 5-15% CaO, 10
１８18% Na ₂ O, 0-5% K ₂ O, 5-15% M
a basic glass composition consisting of gO + CaO and 10-20% of Na ₂ O + K ₂ O; and a coloring component containing 0.46-1.50% of total iron oxide in terms of Fe ₂ O ₃ , and Fe ₂ FeO converted to O ₃ is 22 to 5 of the total iron oxide.
A heat-shielding glass in which a conductive coating consisting essentially of an oxide is formed on the surface of a glass plate having a glass composition of 6%. 2. The method according to claim 1, wherein the conductive film is 1 × 10 ²⁰ to 2 × 1.
An electron concentration of 0 ²¹ cm ^-3 , an electron mobility of 5 to 50 cm ² / Vs, and a film thickness of 5 to 1000 nm.
A heat ray shielding glass according to claim 1. 3. The heat ray shielding glass according to claim 1, wherein the conductive film is a film formed by a pyrolysis method on a surface of a glass ribbon manufactured by a float method. 4. A solar control double-glazing comprising the solar control glass according to claim 1, wherein the surface on which the conductive coating is formed is in contact with a sealed air layer. Heat ray shielding double glazing.