JP2008037671A - Glass plate with infrared shielding film - Google Patents

Abstract

An object of the present invention is to provide a glass plate with an infrared shielding film that is excellent in visible light transmittance, infrared transmittance, radio wave permeability and mechanical durability, and capable of suppressing the absorption of solar energy.
A glass plate, a first infrared shielding film, and a second infrared shielding film, wherein the first infrared shielding film comprises a coating (1) made of a high refractive index inorganic material and a low refractive index. It has a laminated film (X) in which films (2) made of an inorganic material are alternately laminated, and the total of the number of films (1) and the number of films (2) is 3 or more. An infrared shielding film having a geometric thickness of 70 to 150 nm and a geometrical thickness of the coating (2) of 100 to 200 nm. The second infrared shielding film is in a matrix mainly composed of silicon oxide. A glass plate with an infrared shielding film, which is an infrared shielding film having a configuration in which tin-doped indium oxide fine particles having an average primary particle diameter of 100 nm or less are dispersed and having a geometric thickness of 0.2 to 12 μm.
[Selection] Figure 1

Description

  The present invention relates to a glass plate with an infrared shielding film.

In recent years, a glass plate with an infrared shielding film has been adopted for the purpose of shielding infrared rays flowing into a vehicle or building through vehicle glass or architectural glass, and reducing the temperature rise and cooling load in the vehicle or building (for example, , See Patent Document 1). In addition, vehicle glass and architectural glass are often required to have high visible light transmittance in order to ensure safety and visibility.
Many methods have been proposed so far in which infrared ray shielding performance is added to a glass plate to enhance heat ray shielding. For example, those that tried to add infrared shielding performance to the glass plate itself by adding infrared absorbing ions to the glass plate, and those that tried to add infrared shielding performance by forming a conductive film on the glass plate surface were proposed. Has been used in practice.

However, in the method of adding infrared absorbing ions to the glass plate, the infrared absorbing property is increased while keeping the visible light transmittance high, and in particular, the shielding property of the medium wavelength infrared ray having a wavelength of 1.5 to 2.7 μm is increased. It was difficult.
Further, in the method of forming a conductive film on the surface of the glass plate, radio waves cannot pass through the glass because of the conductive film, and the radio transmission of the opening is required with the recent spread of mobile communication. As a result, inconvenience may occur.
Thus, it has been extremely difficult to produce a glass plate having transparency, infrared shielding properties and radio wave transmission properties at the same time.

In order to solve the above-described problems, a coating film in which tin-doped indium oxide fine particles (hereinafter also referred to as “ITO fine particles”) exhibiting high infrared shielding properties are dispersed in a binder is applied to the surface of the glass plate to shield the infrared rays. A method of forming a glass plate with a film has been proposed (see Patent Documents 2 and 3). With this method, it is possible to impart infrared ray shielding properties while maintaining a relatively high visible light transmittance, and it is also possible to impart radio wave permeability because conductivity as a film is suppressed by the presence of a binder. Become.
The binder used in this system is usually an organic binder or an inorganic binder, but the organic binder has a poor mechanical durability of the obtained film, for example, a mechanical durability such as an automotive door glass plate. There was a problem that it could not be used for the required part. On the other hand, a material such as a sol-gel method is often used as an inorganic binder, but the coating is so durable that it can still be used in parts where mechanical durability is required. In order to manufacture, it was necessary to heat-treat at a relatively high temperature, for example, 400 ° C. or higher, preferably 500 ° C. or higher.

  However, since the tin-doped indium oxide conductor is an oxygen-deficient semiconductor, free electrons are lost due to oxidation and the infrared shielding property is lost when the conductor is placed at a temperature of 300 ° C. or higher in the presence of oxygen. . For this reason, in order to produce a coating film that maintains infrared shielding properties and excellent mechanical durability, heat treatment is performed in a non-oxidizing atmosphere, which is overwhelmingly disadvantageous in terms of cost, or a coating film having infrared shielding properties. Further, it is necessary to coat a tin-doped indium oxide anti-oxidation layer on the surface of the film or to contain a large amount of expensive ITO fine particles in the film, which is uneconomical.

JP-A-10-279329 JP-A-7-70482 Japanese Patent Laid-Open No. 8-41441

As a result of earnest research, the inventor has a structure in which ITO fine particles having an average primary particle diameter of 100 nm or less are dispersed in a matrix mainly composed of silicon oxide and containing 2 atomic% or more of nitrogen with respect to Si. By providing an infrared shielding film having a thickness of 200 to 3000 nm on the surface of the glass plate, the visible light transmittance is high, the infrared transmittance is low, the radio wave transmittance is high, and the mechanical durability of a window glass plate for automobiles, etc. It has been found that it can also be applied to sites where high sex is required.
The present inventor has found that when the infrared shielding film is provided, infrared absorption by the ITO fine particles occurs, so that the absorbed solar energy is re-radiated. In this case, for example, when the above-mentioned glass plate with an infrared shielding film is used as a window glass for automobiles or when used as a window glass for buildings, it becomes a problem if solar radiation energy is re-radiated to the vehicle interior or indoor side. Sometimes.
Therefore, the present invention provides a glass plate with an infrared shielding film having a high visible light transmittance, a low infrared transmittance, a high radio wave transmittance, excellent mechanical durability, and suppression of absorption of solar energy. The purpose is to provide.

  As a result of earnest research to achieve the above object, the inventor of the present invention has a high visible light transmittance by providing an infrared shielding film having a specific infrared reflecting performance on the glass plate with an infrared shielding film. It was found that a glass plate with an infrared shielding film having low transmittance, high radio wave permeability, excellent mechanical durability, and capable of suppressing the absorption of solar radiation energy, and completed the present invention. It was.

That is, the present invention provides the following (i) to (ix).
(I) A glass plate with an infrared shielding film having a glass plate, a first infrared shielding film, and a second infrared shielding film,
The first infrared shielding film includes a film (1) made of a high refractive index inorganic material having a refractive index of 1.90 or more and a film (2) made of a low refractive index inorganic material having a refractive index of 1.56 or less. The film has alternating laminated films (X), the total number of the films (1) and the films (2) is 3 or more, and the geometric thickness of the film (1) is 70. An infrared shielding film having a thickness of ˜150 nm and a geometric thickness of the coating (2) of 100 to 200 nm;
The second infrared shielding film has a configuration in which tin-doped indium oxide fine particles having an average primary particle diameter of 100 nm or less are dispersed in a matrix mainly composed of silicon oxide, and has a geometric thickness of 0.2 to 12 μm. A glass plate with an infrared shielding film, which is an infrared shielding film.
(Ii) The glass plate with an infrared shielding film according to (i), wherein at least one of the coating films (1) is a single layer film (1a) of titanium oxide or titanium oxynitride.
(Iii) At least one of the films (1) is a high refractive multilayer film (1b) having a multilayer structure of two or more layers made of different types of high refractive index inorganic materials, and the high refractive multilayer film (1b) The glass plate with an infrared shielding film according to (i) above, wherein at least one layer is a layer of titanium oxide or titanium oxynitride.
(Iv) At least one layer of the high refractive multilayer film (1b) is a layer of titanium oxide or titanium oxynitride, and at least one other layer of the high refractive multilayer film (1b) is a layer of zirconium oxide. The glass plate with an infrared shielding film according to (iii) above.
(V) The multilayer coating (X) is a high refractive index multilayer coating (1b-1) having a total geometric thickness of 70 to 150 nm including a zirconium oxide layer and a titanium oxide or titanium oxynitride layer. The glass plate with an infrared shielding film according to (i) above, comprising two and the coating (2) existing between the two high refractive index multilayer coatings (1b-1).
(Vi) The glass plate with an infrared shielding film according to any one of (i) to (v), wherein the coating (2) is a silicon oxide layer.

(Vii) The second infrared shielding film is tin-doped indium oxide fine particles having an average primary particle diameter of 100 nm or less on the glass plate or the surface of the first infrared shielding film on the glass plate, and oxidized. A silicon compound that can form a silicon gel and an organic solvent, and a dispersion liquid containing 1 to 10% by mass of the tin-doped indium oxide fine particles is applied to the silicon compound and / or the silicon compound. By forming a tin-doped indium oxide fine particle dispersion layer containing a gelled product, and then heating the glass plate at a temperature of 300 ° C. or less, the silicon compound in the tin-doped indium oxide fine particle dispersion layer and / or (I) to (vi), which are infrared shielding films formed by curing the gelled product of the silicon compound. Infrared shielding film-coated glass plate according to any one of.
(Viii) The glass plate with an infrared shielding film according to (vii), wherein the silicon compound is polysilazane.
(Ix) The glass plate with an infrared shielding film according to any one of (i) to (viii), wherein the visible light transmittance defined in JIS R3212: 1998 is 70% or more.

  The glass plate with an infrared shielding film of the present invention has high visible light transmittance, low infrared transmittance, high radio wave permeability, excellent mechanical durability, and suppression of solar energy.

Hereinafter, the present invention will be described in detail.
The glass plate with an infrared shielding film of the present invention is a glass plate with an infrared shielding film having a glass plate, a first infrared shielding film, and a second infrared shielding film, wherein the first infrared shielding film is a glass plate. A laminated film (1) made of a high refractive index inorganic material having a refractive index of 1.90 or more and a film (2) made of a low refractive index inorganic material having a refractive index of 1.56 or less are alternately laminated ( X), the sum of the number of the coating films (1) and the number of the coating films (2) is 3 or more, the geometric thickness of the coating film (1) is 70 to 150 nm, 2) An infrared shielding film having a geometric thickness of 100 to 200 nm, wherein the second infrared shielding film is a tin-doped indium oxide fine particle having an average primary particle diameter of 100 nm or less in a matrix mainly composed of silicon oxide. Has a distributed configuration and geometric thickness An infrared shielding film is 200～3000Nm, an infrared shielding film-coated glass plate.

  The glass plate with an infrared shielding film of the present invention includes a glass plate, a first infrared shielding film, and a second infrared shielding film. The order in which the glass plate, the first infrared shielding film, and the second infrared shielding film are laminated is not particularly limited. That is, the order of the glass plate, the first infrared shielding film, the second infrared shielding film, the first infrared shielding film, the glass plate, the order of the second infrared shielding film, the first infrared shielding film, the second Any of the order of an infrared shielding film and glass may be sufficient.

FIG. 1 is a schematic cross-sectional view showing various examples of the glass plate with an infrared shielding film of the present invention.
A glass plate 1 with an infrared shielding film shown in FIG. 1A has a first infrared shielding film 12 on one surface of a glass plate 10, and a second infrared ray on the first infrared shielding film 12. A shielding film 14 is provided.
A glass plate 2 with an infrared shielding film shown in FIG. 1B has a first infrared shielding film 12 on one surface of the glass plate 10, and a second infrared shielding film on the other surface of the glass plate 10. 14.
The glass plate 3 with an infrared shielding film shown in FIG. 1C has a second infrared shielding film 14 on one surface of the glass plate 10, and the first infrared ray is on the second infrared shielding film 14. A shielding film 12 is provided.

  The glass plates 1 to 3 with an infrared shielding film shown in FIGS. 1 (A) to 1 (C) are all second infrared shielding films when used as window glass for automobiles, window glass for construction, and the like. It is preferable that the first infrared shielding film 12 is positioned outside 14 (an arrangement in which the upper side is the outside in FIG. 1). With this arrangement, since the infrared rays incident from the outside are first reflected by the first infrared shielding film 12, the amount of infrared rays reaching the second infrared shielding film 14 is reduced, and as a result, the second The amount of solar radiation energy absorbed and re-radiated by the infrared shielding film 14 can be suppressed.

The glass plate 1 with an infrared shielding film shown in FIG. 1 (A) has an advantage of being excellent in scratch resistance because both sides are constituted by the glass plate 10 and the second infrared shielding film 14.
Both the glass plate 2 with an infrared shielding film shown in FIG. 1 (B) and the glass plate 3 with an infrared shielding film shown in FIG. 1 (C) before the solar energy enters the glass plate with an infrared shielding film. Since it can be reflected to the outside, there is an advantage that the solar radiation transmittance to the inside can be reduced. Furthermore, since the solar radiation transmittance to the inside is small, colored transparent glass that absorbs infrared rays can be used as the glass plate 10, and in this case, the penetration of infrared rays into the inside (when used as a vehicle window) Can be greatly suppressed.

<Glass plate>
The glass plate is not particularly limited, and examples thereof include a glass plate made of an inorganic glass material and a glass plate made of an organic glass material. When used for window glass for automobiles, particularly windshields and sliding windows, it is preferable to use a glass plate made of an inorganic glass material. Examples of the inorganic glass material include ordinary soda lime glass, borosilicate glass, alkali-free glass, and quartz glass.
As the inorganic glass material, glass that absorbs ultraviolet rays or infrared rays can also be used.
Among them, the visible light transmittance defined in JIS R3212: 1998 is 70% or more, the transmittance of light having a wavelength of 1 μm is 30% or less, and the transmittance of light having a wavelength of 2 μm is 40 to 70%. A glass plate made of an inorganic glass material is preferred.

<First infrared shielding film>
The first infrared shielding film has a film (1) made of a high refractive index inorganic material having a refractive index of 1.90 or more and a film (2) made of a low refractive index inorganic material having a refractive index of 1.56 or less alternately. The total number of the coating films (1) and the coating films (2) is 3 or more, and the geometric thickness of the coating film (1) is 70 to It is an infrared shielding film having infrared reflection performance, having a thickness of 150 nm and a geometric thickness of the coating film (2) of 100 to 200 nm.

In the present invention, the high refractive index inorganic material is an inorganic material having a refractive index higher than that of the glass plate. The refractive index value is 1.90 or more, preferably 2.00 to 2.60, more preferably 2.20 to 2.60 (note that the refractive index value is a wavelength). This is the value at 550 nm, and so on.)
Preferred examples of the high refractive index inorganic material include titanium oxide, zinc oxide, tantalum oxide, zirconium oxide, niobium oxide, tin oxide, titanium nitride, silicon nitride, zirconium nitride, aluminum nitride, titanium oxynitride, and tin oxynitride. It is done.

In the present invention, the low refractive index inorganic material is an inorganic material having a refractive index lower than that of the high refractive index inorganic material. The value of the refractive index is 1.56 or less, preferably 1.40 to 1.56, and more preferably 1.45 to 1.56.
Preferred examples of the low refractive index inorganic material include silicon oxide, MgF ₂ , and composite oxides of silicon oxide and other materials (Al, F, C, B, P, etc.). Among these, silicon oxide, a composite oxide of silicon oxide and Al is preferable, and silicon oxide is more preferable.

In the present invention, the geometric thickness of the coating film (1) (when the coating film (1) is a multilayer film, the total geometric thickness of each layer) is 70 to 150 nm, and 90 to 150 nm. Preferably, it is 100-140 nm.
The geometric thickness of the coating (2) (when the coating (2) is a multilayer film, the total geometric thickness of each layer) is 120 to 220 nm, preferably 150 to 220 nm, and 170 More preferably, it is -200 nm.
Considering the value of the refractive index of the high refractive index inorganic material constituting the film (1) and the value of the refractive index of the low refractive index inorganic material constituting the film (2), the geometric thickness of the film (1) When the thickness and the geometric thickness of the coating (2) are within the above range, the optical thickness of each coating is about one-fourth of the wavelength of infrared rays, and the coating (1) and the coating (2) Infrared rays can be efficiently reflected by the interference action of the laminated coatings (X) laminated alternately.

The order of laminating the film (1) and the film (2) is preferably such that the film (1) is positioned on the outermost side when used as an automotive window glass, an architectural window glass, or the like.
For example, the glass plates 1 to 3 with the infrared shielding film shown in FIGS. 1A to 1C are arranged such that the first infrared shielding film 12 is positioned outside the second infrared shielding film 14. In the case of being used in (an arrangement in which the upper side is the outside in FIG. 1), in the glass plate 1 with an infrared shielding film shown in FIG. 1 (A), from the glass plate 10 side, the coating (1), The film (2), the film (1),... Are preferably laminated alternately, and the glass plate 2 with an infrared shielding film shown in FIG. 1 (B) and the infrared shielding shown in FIG. 1 (C). In the glass plate 3 with a film, it is preferable to laminate | stack alternately with a film (1), a film (2), a film (1) ... from the opposite side to the glass plate 10.

  In the laminated coating (X), the total number of coatings (1) and coatings (2) is 3 or more. Accordingly, there are at least two coatings (1), which may be coatings made of the same material or coatings made of different materials. The same applies to the coating (2). When two or more coatings (2) are present in the first infrared shielding film, they may be coatings made of the same material or coatings made of different materials. Good.

The coating (1) (each of the coatings (1)) may be a single-layer film made of a single high-refractive index inorganic material, or two or more layers made of different types of high-refractive index inorganic materials. It may be a high refractive index multilayer film (1b) having a structure.
When the film (1) is a single layer film, it is preferably a single layer film (1a) of titanium oxide or titanium oxynitride. Titanium oxide is transparent and has an advantage that the film thickness can be reduced because the refractive index is particularly high among high refractive index inorganic materials. Titanium oxynitride is also advantageous because it has a high refractive index. The single-layer film of the titanium oxynitride layer is a film made of only a titanium oxynitride (TiO _x N _y ) layer. When titanium oxynitride is used as the material for the coating (1), the optical properties such as reflectance and transmittance can be improved, so that the amount of nitrogen relative to titanium is preferably 0.1 to 20%.

In the high refractive index multilayer film (1b), it is preferable that at least one layer constituting the high refractive index multilayer film (1b) is a layer of titanium oxide or titanium oxynitride.
Examples of the layer other than the titanium oxide or titanium oxynitride layer include a zirconium oxide layer, a tin oxide layer, a tantalum oxide layer, a zinc oxide layer, and a niobium oxide layer. Of these, a zirconium oxide layer is preferable.

  The high refractive index multilayer film (1b) is preferably a high refractive index multilayer film (1b-1) comprising a zirconium oxide layer and a titanium oxide or titanium oxynitride layer. The stacking order of the zirconium oxide layer and the titanium oxide or titanium oxynitride layer is not particularly limited. An embodiment in which the zirconium oxide layer and the titanium oxide or titanium oxynitride layer are stacked in this order from the outside, the titanium oxide or acid from the outside Examples include stacking the titanium nitride layer and the zirconium oxide layer in this order, but the stacking of the zirconium oxide layer, the titanium oxide layer, and the titanium oxynitride layer in this order from the outside more effectively generates cracks during heat treatment. It is preferable in that it can be suppressed.

  The multilayer coating (X) includes two high refractive index multilayer coatings (1b-1) having a total geometric thickness of 70 to 150 nm including a zirconium oxide layer and a titanium oxide or titanium oxynitride layer; It is preferable to consist of the film (2) which exists between two high refractive index multilayer films (1b-1).

As the coating (1), it is preferable to use a single layer film of titanium oxynitride or a high refractive index multilayer film (1b-1) composed of a zirconium oxide layer and a titanium oxide or titanium oxynitride layer as described above. The reason is as follows.
After the first infrared shielding film is provided on the glass plate or the second infrared shielding film on the glass plate, heat treatment such as bending or strengthening may be performed. Depending on the material of the coating, there is a risk of cracks occurring in the first infrared shielding film due to heat treatment during bending or strengthening. In particular, when the geometric thickness of the entire first infrared shielding film is large (for example, 300 nm or more), there is a great concern about the occurrence of cracks. The occurrence of cracks is considered to be mainly due to the volumetric shrinkage of the film due to crystallization during heat treatment. Therefore, the occurrence of cracks can be suppressed by a technique such as using a film made of a material having a low crystallization rate or suppressing volume shrinkage by using a multilayer film in which different materials are laminated.
Titanium oxynitride is less prone to crystallization during heat treatment than titanium oxide. Therefore, if titanium oxynitride is employed as the constituent material of the coating (1), the occurrence of cracks can be suppressed.
In order to suppress the occurrence of cracks, it is also useful to make the coating (1) a multilayer film, and in particular, it is a multilayer film including a zirconium oxide layer and a titanium oxide or titanium oxynitride layer. preferable.
Most of the zirconium oxide layer is monoclinic during film formation. In addition, the zirconium oxide layer has the same crystal lattice size as the titanium oxide layer, and lattice matching is easy to occur. Since such zirconium oxide layers are adjacent to each other, the lattice is prevented from rearranging and crystallizing inside the titanium oxide layer during heat treatment, so that shrinkage hardly occurs during heat treatment (that is, difficult to crystallize). Can be considered. Therefore, the occurrence of cracks can be suppressed by stacking the zirconium oxide layer and the titanium oxide layer.
A multilayer coating of a zirconium oxide layer and a titanium oxynitride layer is more preferable because both effects can be obtained.

  The coating (2) (in the case where there are a plurality of coatings (2)) may be a single layer film made of a single low refractive index inorganic material, or two or more layers made of different types of low refractive index inorganic materials. It may be a low refractive index multilayer film having a multilayer structure. The film (2) is preferably a single layer film made of a single low refractive index inorganic material, and more preferably a single layer film made of silicon oxide.

The first infrared shielding film has a laminated film (X) in which a film (1) made of a high refractive index inorganic material and a film (2) made of a low refractive index inorganic material are alternately laminated. ) And the number of coatings (2) are 3 or more. The total number is not particularly limited as long as it is 3 or more, but if it is too large, the total film thickness becomes too thick, the durability of the film may be deteriorated, and it is disadvantageous in terms of cost. Preferably there is.
The total of the number of coating films (1) and the number of coating films (2) may be an odd number or an even number, and can be appropriately determined according to the situation in which the glass plate with an infrared shielding film is used. Although it is possible, it is preferably an odd number, more preferably 3, 5, 7 and even more preferably 3 or 5.

  From the viewpoint of improving durability, the geometric thickness (total film thickness) of the entire first infrared shielding film is preferably 200 to 700 nm, and more preferably 300 to 500 nm.

The first infrared shielding film may have a thin film (Y) made of an inorganic material on one or both of the laminated film (X) on the glass plate side and the opposite side.
In the thin film (Y), the geometric thickness of each layer constituting the thin film (Y) is less than 70 nm. The thin film (Y) may have a single layer structure or a multilayer structure.
The thin film (Y) is not a main film for imparting infrared reflection performance, but may affect the infrared reflection performance. Moreover, since it plays the role which determines a reflective color, visible light transmittance, etc., when the thin film (Y) is laminated | stacked, all the films | membranes including a thin film (Y) participate in an optical characteristic.

As a thin film (Y), the film | membrane which adjusts the reflective color etc. of the glass plate with an infrared shielding film of this invention is mentioned, for example.
In order to obtain the desired optical characteristics by simply laminating the coating (1) made of a high refractive index inorganic material and the coating (2) made of a low refractive index inorganic material in order to impart an infrared reflection function, As the number of films to be stacked increases, the options expand. However, as described above, as the total film thickness increases by stacking many films, the durability of the film tends to deteriorate, so an appropriate film configuration is required. .
On the other hand, among many options, there may be a case where a maximum and minimum wave (hereinafter referred to as “ripple”) is generated in the reflection spectrum in the wavelength region of 400 to 800 nm, particularly 400 to 600 nm. When ripple occurs, the wavelength of the reflection (transmission) maximum shifts due to in-plane film thickness variation (unevenness), and the reflected (transmitted) color, i.e., color unevenness (irradiance), is detected by the eyes. As a result, the reflected color may be distributed and the infrared reflection performance may be deteriorated.
Therefore, by forming a thin film (Y) on the inner glass side of the laminated coating (X), it is possible to obtain good optical characteristics, while maintaining the solar reflectance (Re) at about 40% or less. A ripple in the spectrum can be suppressed, and a glass plate with an infrared shielding film having a good appearance can be obtained.

Since the thin film (Y) formed for this purpose preferably has an interference action, it preferably has a multilayer structure, and the difference in refractive index between the thin film (Y) layer and the laminated film (X) that are in contact with each other. Is preferably 0.3 or more, and more preferably 0.5 or more. Specifically, a high refractive index layer (c) having a geometric thickness of 5 to 40 nm made of a high refractive index inorganic material having a refractive index of 1.90 or more and a low refractive index inorganic material having a refractive index of 1.56 or less. A low refractive index layer (d) having a geometric thickness of 5 to 40 nm made of a material is alternately laminated, the total number of layers is an even number, and the layer in contact with the film (1) of the laminated film (X) is low. The refractive index layer (d) is preferred.
Examples of the high refractive index layer (c) include a titanium oxide layer, a titanium oxynitride layer, a tin oxide layer, and a zinc oxide layer. Among these, a titanium oxide layer is preferable. Preferable examples of the low refractive index layer (d) include a silicon oxide layer, MgF ₂ , composite oxides of silicon oxide and other materials (Al, F, C, B, P, etc.). Among these, silicon oxide, a composite oxide of silicon oxide and Al is preferable, and silicon oxide is more preferable.

  As the first infrared shielding film, the following embodiments [1] to [8] are preferably exemplified. Especially, the aspect of [2]-[4] and [6]-[8] are preferable at the point which can maintain the durability of a film | membrane, suppressing a ripple effectively, The aspect of [2] and [3] is preferable. More preferred is the embodiment [3]. In the following examples, the coating (1) made of a high refractive index inorganic material in the laminated coating (X) is represented by H, and the coating (2) made of a low refractive index inorganic material is represented by L. The high refractive index layer in the thin film (Y) is represented by H ′, and the low refractive index layer is represented by L ′. Furthermore, the stacking order from the outside is represented by a subscript.

[1]: outer) [multilayer coating _{(X) (H 1 / L} 2 / H 3)] ( inside)
[2]: (Outside) [Thin film (Y) (H ′ ₁ / L ′ ₂ )] / [Laminated coating (X) (H ₃ / L ₄ / H ₅ )] (Inside)
[3]: outer) [multilayer coating _{(X) (H 1 / L} 2 / H 3)] / [ film _{(Y) (L '4 /} H' 5)] ( inside)
[4]: (Outside) [Thin film (Y) (H ′ ₁ / L ′ ₂ )] / [Laminated coating (X) (H ₃ / L ₄ / H ₅ )] (Inside)
[5]: outer) [multilayer coating _{(X) (H 1 / L} 2 / H 3 / L 4 / H 5)] ( inside)
[6]: (outside) [thin film (Y) (H ′ ₁ / L ′ ₂ )] / [laminated coating (X) (H ₃ / L ₄ / H ₅ / L ₆ / H ₇ )] (inside)
[7]: outer) [multilayer coating _{(X) (H 1 / L} 2 / H 3 / L 4 / H 5)] / [ film _{(Y) (L '6 /} H' 7)] ( inside)
[8]: (Outside) [Thin film (Y) (H ′ ₁ / L ′ ₂ )] / [Laminated coating (X) (H ₃ / L ₄ / H ₅ / L ₆ / H ₇ )] / [Thin film ( _{Y) (L '8 / H} ' 9)] ( inside)

  By configuring the first infrared shielding film as described above, while ensuring the radio wave transmission of the glass plate with the infrared shielding film of the present invention, it is possible to increase the solar reflectance and reduce the solar transmittance, Excellent durability.

The first infrared shielding film preferably has sufficient radio wave permeability since the glass plate with the infrared shielding film of the present invention is suitably used for a vehicle window.
Specifically, it is preferable that the sheet resistance value of the first infrared shielding film is 1 kΩ / □ or more. Since the larger the sheet resistance value, the better, the upper limit is not particularly limited. Further, the material forming the first infrared shielding film has a sheet resistance value larger than the sheet resistance value before the heat treatment because the oxidation of the material proceeds when the material is subjected to the heat treatment.

After the first infrared shielding film is provided on the glass plate or the second infrared shielding film on the glass plate, heat treatment such as bending or strengthening may be performed. The heat treatment can be performed according to conditions employed in normal bending and strengthening. For example, it is performed under conditions of a set temperature of 650 ° C. and a heat treatment time of 15 minutes.
The method of providing the first infrared shielding film on the glass plate or the second infrared shielding film on the glass plate is not particularly limited. For example, the coating (1) and the coating (2) can be formed by a known method. A method of laminating alternately in order to form a laminated film (X), and laminating a thin film (Y) on one or both of the glass sheet side and the opposite side of the laminated film (X) as needed. Although a well-known method is not specifically limited, Sputtering method is preferable.

  When heat treatment is performed, the structure before the heat treatment is preferably the same as the structure after the heat treatment. However, when titanium oxynitride is subjected to heat treatment, nitrogen atoms in the material are released from the film as a gas such as nitrogen gas. Therefore, the nitrogen content of the titanium oxynitride layer in the coating (1) before heat treatment is usually larger than the nitrogen content of the coating (1) after heat treatment, and the amount of nitrogen relative to titanium is 0.1 to 80%. It is preferable that it is 2 to 40%, more preferably 3 to 40%. When the amount of nitrogen with respect to titanium is in the above range, the refractive index change before and after the heat treatment is small, and the effect of suppressing the generation of cracks during the heat treatment becomes large.

Examples of the sputtering method include a DC (direct current) sputtering method, an AC (alternating current) sputtering method, a high frequency sputtering method, and a magnetron sputtering method. Among them, the DC magnetron sputtering method and the AC magnetron sputtering method are preferable because the process is stable and the film can be easily formed on a large area.
The material of the target and the composition of the sputtering gas are appropriately selected depending on the type of film to be formed. Further, the sputtering conditions (pressure, temperature, etc.) are appropriately determined depending on the type and thickness of the film to be formed. The total pressure of the sputtering gas may be a pressure at which glow discharge is stably performed.

<Second infrared shielding film>
The second infrared shielding film has a configuration in which ITO fine particles having an average primary particle diameter of 100 nm or less are dispersed in a matrix mainly composed of silicon oxide, and has a geometric thickness of 0.2 to 12 μm. It is a membrane.

The ITO fine particles used for the second infrared shielding film impart infrared shielding properties to the glass plate with the infrared shielding film.
The ITO fine particles have an average primary particle diameter of 100 nm or less. Within the above range, clouding (cloudiness value, haze) due to scattering is less likely to occur when the second infrared shielding film is formed. The average primary particle diameter of the ITO fine particles is preferably 5 to 65 nm in terms of maintaining transparency.
As for the mixing ratio of tin oxide and indium oxide in the ITO fine particles, the number of indium atoms relative to the number of tin atoms (In / Sn) is preferably 2 to 20, and more preferably 3 to 10.

The matrix used for the second infrared shielding film is a matrix mainly composed of silicon oxide (hereinafter also referred to as “silicon oxide matrix”). Here, the silicon oxide matrix is a matrix containing 50 mol% or more of silicon oxide. The silicon oxide matrix functions as a binder for the above-mentioned ITO fine particles to increase the film hardness, and has a function of imparting adhesion to the glass plate of the second infrared shielding film or the first infrared shielding film on the glass plate. .
Among these, it is preferable that nitrogen is contained in the silicon oxide matrix. The present inventor speculates that nitrogen atoms may have a reducing action in the ITO fine particle film, and as a result, even if the amount of ITO fine particles used is small, high infrared shielding properties are achieved. is doing.
When nitrogen is contained in the silicon oxide matrix, the content of nitrogen atoms is preferably 2 atom% or more, more preferably 3 atom% or more, and more preferably 5 atoms relative to the silicon atoms in the silicon oxide. % Or more is more preferable.
In addition, the content of nitrogen atoms in the silicon oxide matrix is 20 atomic% or less with respect to the silicon atoms in the silicon oxide. This is preferable in that the adhesion to the infrared shielding film is excellent.

When the ITO fine particles are continuously adhered in the second infrared shielding film, the ITO fine particles themselves are excellent in conductivity, so that the second infrared shielding film itself develops conductivity and adversely affects radio wave transmission. The silicon oxide matrix has the effect of dispersing the ITO fine particles, suppressing the contact between the ITO fine particles, and preventing the second infrared shielding film from becoming a conductive film.
The silicon oxide matrix may be a matrix material containing Si—O—Si bonds. When nitrogen is contained in the silicon oxide matrix, for example, some nitrogen atoms may be unevenly distributed on the surface of the ITO fine particles. The matrix material may contain nitrogen atoms bonded to silicon atoms. That is, a part of silicon oxide in the matrix material may be silicon oxynitride.

Furthermore, a part of silicon oxide in the matrix material may be replaced with titanium oxide. Titanium oxide serves to help cure the second infrared shielding film at a low temperature, and about 50 mol% or less of silicon oxide in the matrix material can be replaced with titanium oxide. Here, “titanium oxide” does not need to be TiO ₂ in a strict sense, and preferably forms a matrix material containing a Ti—O—Ti bond or a Si—O—Ti bond. A part of the titanium oxide may be unevenly distributed on the surface of the ITO fine particles. Further, the matrix material may contain nitrogen atoms bonded to titanium atoms.

  Further, the matrix material may contain a minor component of about 5% by mass or less, for example, elements such as C, Sn, Zr, Al, B, P, Nb, and Ta.

The amount of the ITO fine particles in the second infrared shielding film is preferably 0.2 g / m ² or more. Within the above range, the infrared shielding performance is excellent.
The amount of ITO fine particles in the second infrared shielding film is preferably 1.0 g / m ² or less, more preferably 0.7 g / m ² or less. Within the above range, the cost can be reduced without impairing the infrared shielding performance and transparency.

The content ratio ([ITO fine particles] / [matrix]) of the ITO fine particles and the matrix in the second infrared shielding film is preferably 10/90 or more, and more preferably 20/80 or more in terms of mass ratio. More preferred. Within the above range, the infrared shielding properties are excellent.
The content ratio between the ITO fine particles and the matrix in the second infrared shielding film is preferably 45/55 or less, and more preferably 40/60 or less in terms of mass ratio. Within the above range, it is easy to maintain radio wave permeability while maintaining the adhesion and hardness of the second infrared shielding film.

The geometric thickness of the second infrared shielding film is 0.2 μm or more, preferably 0.4 μm or more, and more preferably 0.5 μm or more. Within the above range, the infrared shielding properties are excellent.
The geometric thickness of the second infrared shielding film is 12 μm or less, and preferably 10 μm or less. Within the above range, cracks are unlikely to form when the second infrared shielding film is formed, and the visible light transmittance does not decrease.
This geometric thickness can be measured, for example, by observing a cross section of the second infrared shielding film with a scanning electron microscope.

The method of providing the second infrared shielding film on the glass plate or the first infrared shielding film on the glass plate is not particularly limited, but a suitable production method is exemplified below.
That is, first, on the glass plate or the surface of the first infrared shielding film on the glass plate, ITO fine particles having an average primary particle diameter of 100 nm or less and a silicon compound capable of forming a silicon oxide gel (hereinafter simply referred to as “ A dispersion containing 1 to 10% by mass of the ITO fine particles, and coating the silicon compound and / or the gelled product of the silicon compound. The ITO fine particle dispersion layer is formed, and then the glass plate is heated at a temperature of 300 ° C. or less, whereby the silicon compound and / or the gel compound of the silicon compound in the ITO fine particle dispersion layer is obtained. This is a method of forming a second infrared shielding film by curing.

Since the aggregation state of the ITO fine particles in the second infrared shielding film obtained by curing the ITO fine particle dispersion layer reflects the aggregation state in the dispersion liquid, the transparency and radio wave transmittance of the second infrared shielding film are improved. In order to maintain, it is preferable that the ITO fine particles are highly dispersed in the dispersion.
As the dispersion state, the number average particle diameter of the aggregates of ITO fine particles is preferably 500 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less (substantially monodispersed state).
The type of the organic solvent that serves as the dispersion medium is not particularly limited as long as it can dissolve the silicon compound. Specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, esters, ethers, and halogenated hydrocarbons. These organic solvents are used alone or in combination.
The method for dispersing is not particularly limited, and for example, a known method can be used. Specific examples include ultrasonic irradiation, a homogenizer, a ball mill, a bead mill, a sand mill, a media mill (for example, a paint shaker), and a high-pressure impact mill (for example, a jet mill and a nanomizer).

Here, as the ITO fine particles in the dispersion, known ones can be used. The crystal system of the ITO fine particles is not limited to ordinary cubic crystals, and hexagonal crystals that are generally said to be inferior in infrared shielding properties can also be used.
The dispersion contains 1 to 10% by mass of ITO fine particles. By containing 1% by mass or more of the ITO fine particles in the dispersion liquid, a second infrared shielding film having a desired infrared shielding performance can be easily obtained by a single film forming process. Further, when the content of ITO fine particles in the dispersion is 10% by mass or less, the stability of the dispersion is excellent.

The silicon compound is a component (hereinafter also referred to as “siloxane matrix material”) that can be converted into a silicon oxide matrix having a siloxane bond by heating.
Specifically, for example, alkoxysilanes used in the sol-gel method, or a partially hydrolyzed product or partially hydrolyzed condensate thereof, water glass, and silicone can be used. Moreover, when nitrogen is contained in the silicon oxide matrix, polysilazane, nitrogen-containing silicone resin, nitrogen-containing silane coupling agent (for example, aminosilane), and partial hydrolysates thereof can be used. Among these, polysilazane is preferable because the durability of the second infrared shielding film can be enhanced to a high degree.

Polysilazane is a line having a structure represented by the chemical formula: —SiR ¹ ₂ —NR ² —SiR ¹ ₂ — (wherein R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group). It is a general term for a shape or a cyclic compound. Polysilazane is a material in which Si—NR ² —Si bonds are decomposed by heating or reaction with moisture to form a Si—O—Si network.
Compared to a silicon oxide-based film obtained from tetraalkoxysilane or the like, a silicon oxide-based film obtained from polysilazane has higher mechanical durability and gas barrier properties. Note that the above reaction usually does not proceed completely when heated to about 300 ° C., and nitrogen remains in the film in a Si—N—Si bond or other bond form, and at least a portion of silicon oxynitride is generated. It is thought that. Further, the mass ratio (such as mass ratio [ITO fine particles] / [SiO ₂ ] described later) of silicon oxide containing nitrogen atoms is a numerical value calculated assuming that all silicon atoms are silicon atoms of silicon oxide ( (Numerical value converted to silicon oxide).
The polysilazane is a perhydropolysilazane in which R ¹ and R ² are both hydrogen atoms in the above chemical formula, and a partial organic in which R ¹ is a hydrocarbon group such as a methyl group in the above chemical formula, and R ² is a hydrogen atom. Polysilazane and mixtures thereof are preferred. When these polysilazanes are used, the mechanical strength and oxygen barrier properties of the second infrared shielding film are increased. Of these, perhydropolysilazane is preferable.

The content ratio of the ITO fine particles to the silicon compound ([ITO fine particles] / [SiO ₂ ]) in the dispersion is preferably 10/90 to 45/55 by mass ratio. When the content ratio is 10/90 or more, it is easy to obtain a second infrared shielding film having a desired infrared shielding performance by a single film formation process. On the other hand, when the content ratio is 45/55 or less, the dispersibility of the ITO fine particles in the second infrared shielding film can be enhanced, and the cost can be reduced.

The dispersion may contain a titanium compound that can form a titanium oxide gel. As the titanium compound, an organic titanium compound is preferable. The organic titanium compound has a function of accelerating the curing of the silicon compound in the curing step described later, and can exhibit mechanical strength by curing at a lower temperature.
Examples of the organic titanium compound include a tetraalkoxy titanium compound, a titanium chelate compound, a titanium acylate compound, and a titanate coupling agent. Among these, a tetraalkoxy titanium compound and a titanium chelate compound are preferable.
As the tetraalkoxytitanium compound, a compound represented by the general formula: Ti (OR ′) ₄ (wherein R ′ represents a hydrocarbon group having 1 to 8 carbon atoms) is preferable. Specific examples include tetra-n-butoxy titanium, tetraisopropoxy titanium, tetramethoxy titanium, tetraethoxy titanium, and tetrakis (2-ethylhexyloxy) titanium.
As the titanium chelate compound, a chelate compound of titanium alkoxide is preferable. Specifically, diisopropoxybis (ethylacetoacetate) titanium, di-n-butoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetonato) titanium, di-n-butoxybis (acetylacetonato) titanium And tetraacetylacetonate titanium.
Titanium compounds include diisopropoxybis (ethylacetoacetate) titanium, di-n-butoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetonato) titanium, di-n-butoxybis in terms of handling. (Acetylacetonato) titanium is preferred. The titanium compound may be added after the preparation of the dispersion, or may be added at the stage of preparing the dispersion.

The dispersion obtained as described above is coated on the glass plate or the surface of the first infrared shielding film on the glass plate to form an ITO fine particle dispersion layer.
The application method is not particularly limited, and examples thereof include dip coating, spin coating, spray coating, flexographic printing, screen printing, gravure printing, roll coating, meniscus coating, and die coating.
After coating, it is preferable to dry the coating film at a temperature of 200 ° C. or lower before performing the heat curing step described later. In this drying step, the main purpose is to remove the solvent component and the like in the coating film, and even if the temperature is raised above 200 ° C., it is not so effective, so it becomes uneconomical. The drying time is preferably about 30 seconds to 2 hours. The atmosphere during drying may be in the air or a non-oxidizing atmosphere, but the effect of using the non-oxidizing atmosphere cannot be particularly expected. In addition, it is also possible to perform this drying process under reduced pressure. In that case, the ultimate vacuum is preferably about 0.10 to 10 kN / m ² , and the treatment time is preferably 10 seconds to 30 minutes.
The heat curing step may be performed without going through this drying step, and in the heat curing step shown below, the coating film may be dried simultaneously with the curing.

After the ITO fine particle dispersed layer is formed as described above, the glass plate is heated at a temperature of 300 ° C. or lower to cure the silicon compound and form the second infrared shielding film. The curing time is usually about 30 seconds to 10 hours.
When polysilazane is used as the silicon compound, curing with moisture in the atmosphere is possible in addition to the heat treatment. That is, curing proceeds by holding for 10 minutes to several days at a humidity of about 80% or more, or for several days to several weeks at a humidity of 40 to 80%, and the second infrared shielding with sufficient strength. A film can be formed.

  According to the preferred manufacturing method described above, the second infrared shielding film having high durability can be efficiently and economically produced on the glass plate or the first infrared shielding film without firing at a high temperature. can do. At this time, a second infrared shielding film can be provided on the tempered glass obtained by heating the glass plate made of an inorganic glass material to a temperature close to 650 to 700 ° C. in the atmosphere, quenching it, and performing a tempering treatment. For example, a glass plate with an infrared shielding film having high durability can be efficiently and economically manufactured. Therefore, the glass plate with an infrared shielding film 2 shown in FIG. 1 (B) and FIG. 1 (C). It is suitable when producing the shown glass plate 3 with an infrared shielding film.

<Glass plate with infrared shielding film>
The glass plate with an infrared shielding film of the present invention can be obtained by laminating the above-described first infrared shielding film and the above-described second infrared shielding film on the above-described glass plate by the above-described method.

When the glass plate with an infrared shielding film of the present invention is used as a window glass plate for automobiles, a high visible light transmittance may be required depending on the part. For that purpose, it is specified in JIS R3212: 1998. The visible light transmittance of the glass plate with an infrared shielding film is preferably 70% or more.
Moreover, transparency is important not only for automobile window glass plates but also for ordinary window glass plates. For this purpose, the glass plate with an infrared shielding film of the present invention preferably has a haze value of less than 1.0% as a glass plate with an infrared shielding film.

  The use of the glass plate with an infrared shielding film of the present invention is not particularly limited, and can be used for a wide range of uses. For example, automobile windows (for example, windshields, roof windows, elevating windows, side fixed windows, backlights, roof windows), vehicle windows such as railway vehicle windows; architectural windows.

The result of having obtained the optical characteristic by simulation about the glass plate with an infrared shielding film produced like the following example is demonstrated below. However, the present invention is not limited to these.
1. Examples 1 and 2 (Example of glass plate with infrared shielding film having the structure shown in FIG. 1A)
(1) Glass plate 10
As the glass plate 10, FL3 shown below is used.
FL3: colorless and transparent soda lime silica glass, manufactured by Asahi Glass Co., Ltd., thickness 3.0 mm, length 100 mm × width 100 mm

(2) First infrared shielding film 12
A first infrared shielding film 12 (first film example 1 or first film example 2) having the following configuration is formed from the glass plate 10 side. In addition, the numerical value in parenthesis shows the geometric thickness of each layer.
First film example 1: (glass plate) / ZrO ₂ (15 nm) / TiO _x N _y (105 nm) / SiO ₂ (185 nm) / ZrO ₂ (15 nm) / TiO _x N _y (105 nm) / SiO ₂ (30 nm ) / TiO ₂ (10 nm)
First film example 2: (glass plate) / ZrO ₂ (15 nm) / TiO _x N _y (95 nm) / SiO ₂ (130 nm) / ZrO ₂ (15 nm) / TiO _x N _y (95 nm)

Each layer can be formed as follows. In the formation of the first ZrO ₂ layer, the object to be processed is the glass plate 10, and in the subsequent formation of each layer, the object to be processed is a glass plate having the layers formed so far.

<ZrO ₂ layer>
A Zr target is placed on the cathode as a sputtering target in the vacuum chamber, and the vacuum chamber is evacuated to 2.0 × 10 ⁻³ Pa or less. Then, oxygen gas 60 sccm and argon gas 140 sccm are introduced as sputtering gas. At this time, the pressure is 3.0 × 10 ⁻¹ Pa. In this state, a reactive sputtering method is performed using a DC pulse power source to form a ZrO ₂ layer on the object to be processed installed in the vacuum chamber.

<TiO _x N _y layer>
A TiO _x (1 <x <2) target is placed on the cathode as a sputtering target in the vacuum chamber, and the vacuum chamber is evacuated to 2.0 × 10 ⁻³ Pa or less. Then, argon gas 270 sccm, nitrogen gas 20 sccm, and oxygen gas 12 sccm are introduced as sputtering gases. At this time, the pressure is 4.2 × 10 ⁻¹ Pa. In this state, a reactive sputtering method is performed using an AC power source to form a TiO _x N _y layer on the object to be processed installed in the vacuum chamber.

<SiO ₂ layer>
A SiAl (Al: 10%) target is placed on the cathode as a sputtering target in the vacuum chamber, and the vacuum chamber is evacuated to 2.0 × 10 ⁻³ Pa or less. Then, argon gas 210 sccm and oxygen gas 190 sccm are introduced as sputtering gas. At this time, the pressure is 3.4 × 10 ⁻¹ Pa. In this state, a reactive sputtering method is performed using an AC power source to form a SiO ₂ layer on the object to be processed installed in the vacuum chamber.

<TiO ₂ layer>
A TiO _x (1 <x <2) target is placed on the cathode as a sputtering target in the vacuum chamber, and the vacuum chamber is evacuated to 2.0 × 10 ⁻³ Pa or less. Then, argon gas 280 sccm and oxygen gas 20 sccm are introduced as sputtering gas. At this time, the pressure is 4.3 × 10 ⁻¹ Pa. In this state, a reactive sputtering method is performed using an AC power source to form a TiO ₂ layer on the object to be processed installed in the vacuum chamber.

  Hereinafter, the refractive indexes of the materials constituting each layer are shown in Table 1. This value is a value at a wavelength of 550 nm.

  The glass plate with the first infrared shielding film obtained above is placed in a small belt furnace, and heat treatment is performed under conditions of a set temperature of 650 ° C. and a heat treatment time of 15 minutes.

(3) Second infrared shielding film 14
On the 1st infrared shielding film 12 of the glass plate with a 1st infrared shielding film obtained in this way, a 2nd infrared shielding film is produced with the following method.
0.71 g of xylene dispersion A in which 30% by mass of cubic ITO fine particles having a primary particle size of 40 nm (manufactured by Fuji Titanium Industry Co., Ltd.) are dispersed, 20% by mass of perhydropolysilazane (manufactured by AZ-Electronic Materials, 2.15 g of xylene solution B containing trade name: Aquamica NP-110) is weighed, mixed at room temperature, and stirred for 10 minutes to obtain coating solution C.
The obtained coating liquid C is applied on the first infrared shielding film of the glass plate with the first infrared shielding film obtained as described above by spin coating, and dried in the atmosphere at 100 ° C. for 10 minutes. And curing for 30 minutes in an oven maintained at 210 ° C. to obtain a second infrared shielding film (second film example 1). These steps are repeated several times to obtain a second infrared shielding film having a geometric thickness of 10 μm.
In this way, a glass plate with an infrared shielding film having the structure shown in FIG.

The structure of the glass plate with an infrared shielding film of Examples 1 and 2 is as follows.
Example 1: (outside) FL3 / first film example 1 / second film example 1 (inside)
Example 2: (Outside) FL3 / first film example 2 / second film example 1 (inside)

2. Examples 3 to 6 (examples of glass plates with an infrared shielding film having the structure shown in FIG. 1B)
(1) Glass plate 10
As the glass plate 10, UVFL3 shown below is used.
UVFL3: Green colored transparent soda lime silica glass, manufactured by Asahi Glass Co., Ltd., thickness 3.0 mm, length 100 mm × width 100 mm

(2) First infrared shielding film 12
In the same manner as in Example 1, the first infrared shielding film 12 (first film example 3 and first film example 4) having the following configuration is formed from the glass plate 10 side. In addition, the numerical value in parenthesis shows the geometric thickness of each layer.
First film example 3: (glass plate) / TiO ₂ (10 nm) / SiO ₂ (30 nm) / ZrO ₂ (15 nm) / TiO _x N _y (105 nm) / SiO ₂ (185 nm) / ZrO ₂ (15 nm) / TiO _x N _y (105 nm) / SiO ₂ (500 nm)
First film example 4: (glass plate) / ZrO ₂ (15 nm) / TiO _x N _y (95 nm) / SiO ₂ (130 nm) / ZrO ₂ (15 nm) / TiO _x N _y (95 nm) / SiO ₂ (23 nm )

(3) Second infrared shielding film 14
On the surface of the glass plate 10 opposite to the first infrared shielding film 12, the number of times of application of the coating liquid C is reduced compared to the method of Example 1, and the second infrared shielding film 14 (second A film example 2) or a second infrared shielding film 14 (second film example 3) having a thickness of 1 μm is provided.
In this way, a glass plate with an infrared shielding film having the structure shown in FIG. 1B is obtained.

The structure of the glass plate with an infrared shielding film of Examples 3 to 6 is as follows.
Example 3: (Outside) first film example 3 / UVFL3 / second film example 2 (inside)
Example 4: (Outside) first film example 3 / UVFL3 / second film example 3 (inside)
Example 5: (Outside) first film example 4 / UVFL3 / second film example 2 (inside)
Example 6: (Outside) first film example 4 / UVFL3 / second film example 3 (inside)

3. Examples 7 to 10 (example of glass plate with infrared shielding film having the structure shown in FIG. 1C)
(1) Glass plate 10
As the glass plate 10, the same UVFL3 as in Examples 3 to 6 is used.

(2) Second infrared shielding film 14
A second infrared shielding film 14 (second film example 2) having a thickness of 0.25 μm or a second infrared shielding film having a thickness of 1 μm is formed on the glass plate 10 in the same manner as in Examples 3 to 6. 14 (second film example 3) is provided.

(3) First infrared shielding film 12
The first infrared shielding film 12 (first film) is the same as in Examples 3 to 6 except that the object to be processed in the formation of the first ZrO ₂ layer is the second infrared shielding film 14 provided on the glass plate 10. Example 3 or first film example 4) is formed.
In this way, a glass plate with an infrared shielding film having the structure shown in FIG. 1C is obtained.

The structure of the glass plate with an infrared shielding film of Examples 7 to 10 is as follows.
Example 7: (outside) first film example 3 / second film example 2 / UVFL3 (inside)
Example 8: (outside) first film example 3 / second film example 3 / UVFL3 (inside)
Example 9: (outside) first film example 4 / second film example 2 / UVFL3 (inside)
Example 10: (outside) first film example 4 / second film example 3 / UVFL3 (inside)

4). Optical Properties of Glass Plate with Infrared Shielding Film For the glass plates with infrared shielding film (Examples 1 to 10) obtained in this way, (1) Visible light transmittance (Tv) by simulation according to the provisions of JIS R3106: 1998 ), (2) top surface solar reflectance (top surface Re), (3) solar radiation transmittance (Te), and (4) solar radiation absorption rate (Ae).
Ae was calculated from Te obtained at the above wavelengths and the upper surface Re, assuming that Ae at each wavelength was Ae = 1− (Re + Te). Strictly speaking, the light incident on the laminated glass has “scattering” in addition to “reflection”, “absorption”, and “transmission”. However, in the case of a glass article, loss due to “scattering” is extremely small, so Ae is 1− (Re + Te ) Is reasonable. This also applies to the absorptance at each wavelength.

As is apparent from Table 2, the glass plate (Examples 1 and 2) having the first infrared shielding film and the second infrared shielding film, even when a colorless and transparent soda lime silica glass is used, has a Te content of 60%. The Ae in this case can be kept low.
Moreover, the glass plate with an infrared shielding film of Examples 3 to 10 using a green colored transparent soda lime silica glass has a Re of 20% or more even though a glass plate with high infrared absorption performance is used. And Ae can be 35% or less. In particular, the glass plates with infrared shielding films of Examples 5 and 9 can reduce Te to around 40% and Ae to 30% or less. When used as a window, it is possible to effectively prevent re-radiation of heat into the vehicle).

It is a schematic sectional drawing which shows the various examples of the glass plate with an infrared shielding film of this invention.

Explanation of symbols

1, 2, 3 Glass plate with infrared shielding film 10 Glass plate 12 First infrared shielding film 14 Second infrared shielding film

Claims (9)

A glass plate with an infrared shielding film having a glass plate, a first infrared shielding film, and a second infrared shielding film,
The first infrared shielding film includes a film (1) made of a high refractive index inorganic material having a refractive index of 1.90 or more and a film (2) made of a low refractive index inorganic material having a refractive index of 1.56 or less. The film has alternating laminated films (X), the total number of the films (1) and the films (2) is 3 or more, and the geometric thickness of the film (1) is 70. An infrared shielding film having a thickness of ˜150 nm and a geometric thickness of the coating (2) of 100 to 200 nm;
The second infrared shielding film has a configuration in which tin-doped indium oxide fine particles having an average primary particle diameter of 100 nm or less are dispersed in a matrix mainly composed of silicon oxide, and has a geometric thickness of 0.2 to 12 μm. A glass plate with an infrared shielding film, which is an infrared shielding film.   The glass plate with an infrared shielding film according to claim 1, wherein at least one of the coating films (1) is a single layer film (1a) of titanium oxide or titanium oxynitride.   At least one of the films (1) is a high refractive multilayer film (1b) having a multilayer structure of two or more layers made of different types of high refractive index inorganic materials, and at least one of the high refractive multilayer films (1b) The glass plate with an infrared shielding film according to claim 1, wherein the layer is a layer of titanium oxide or titanium oxynitride.   The at least one layer of the high refractive multilayer film (1b) is a layer of titanium oxide or titanium oxynitride, and the other at least one layer of the high refractive multilayer film (1b) is a layer of zirconium oxide. 3. A glass plate with an infrared shielding film as described in 3.   The multilayer coating (X) includes two high refractive index multilayer coatings (1b-1) having a total geometric thickness of 70 to 150 nm including a zirconium oxide layer and a titanium oxide or titanium oxynitride layer; The glass plate with an infrared shielding film according to claim 1, comprising the coating film (2) present between the two high-refractive-index multilayer coating films (1 b-1).   The glass plate with an infrared shielding film according to any one of claims 1 to 5, wherein the coating (2) is a layer of silicon oxide.   On the surface of the first infrared shielding film on the glass plate or the glass plate, the second infrared shielding film comprises tin-doped indium oxide fine particles having an average primary particle diameter of 100 nm or less, and a silicon oxide gel. Applying a dispersion containing a silicon compound that can be formed and an organic solvent, wherein the content of the tin-doped indium oxide fine particles is 1 to 10% by mass, The tin-doped indium oxide fine particle dispersion layer is formed, and then heated at a temperature at which the glass plate has a temperature of 300 ° C. or less, whereby the silicon compound and / or the silicon compound in the tin-doped indium oxide fine particle dispersion layer is heated. It is an infrared shielding film formed by hardening | curing the gelled material of any one of Claims 1-6. Infrared shielding film-coated glass plate.   The glass plate with an infrared shielding film according to claim 7, wherein the silicon compound is polysilazane.   The glass plate with an infrared shielding film according to any one of claims 1 to 8, wherein a visible light transmittance defined in JIS R3212: 1998 is 70% or more.

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