JP2017145162A - Infrared absorbing glass article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass article with a coating film, which maintains the sensitivity of an infrared camera while holding infrared absorbing performance.SOLUTION: The ultraviolet and infrared absorbing glass article includes a glass plate and an ultraviolet and infrared absorbing film provided on one main surface of the glass plate. The ultraviolet and infrared absorbing film is mainly composed of silica and contains an ultraviolet absorber and fine particles. The fine particles contain at least one kind selected from tin-doped indium oxide and antimony-doped tin oxide. The ultraviolet and infrared absorbing glass article has an average transmittance at a wavelength of 1,000 nm of 18-30% and an average transmittance at a wavelength of 1,500 nm of 25-40%. The glass plate has a plate thickness of 2.8-5.5 mm.SELECTED DRAWING: None

Description

The present invention relates to a coated glass article that maintains the high sensitivity of an infrared camera while maintaining infrared absorption performance.

From the viewpoint of driving assistance during parking or retreating, the mounting of in-vehicle cameras is increasing, and an infrared camera may be mounted. Conventionally, the camera was mounted only on the windshield and rear glass, but in the future, it is expected that autonomous cars will come out, so it will also be mounted on the side glass where the camera has not been mounted so far. there is a possibility.
As the side glass, for the purpose of absorbing infrared rays, a glass with a film having infrared absorption performance is increasing. In the side glass with a film having the current infrared absorption performance, since the infrared transmittance of the wavelength used for the infrared camera is not sufficient, it is difficult to maintain the high sensitivity of the infrared camera. When the infrared absorbing ability of the coated side glass is reduced, the sensitivity of the infrared camera is improved, but infrared rays are transmitted more and the interior of the vehicle becomes hot. Since more comfort is required for automatic driving, it is ideal that the infrared camera operates with high sensitivity while maintaining infrared absorption performance.

For example, there exists a side glass with a film which has an ultraviolet-ray and infrared absorption capability like patent document 1. FIG. However, the conventional technology is not designed to increase the infrared transmittance at a specific wavelength for the purpose of maintaining the high sensitivity of the infrared camera.

For this reason, when an infrared camera is mounted on a conventional side glass, there is a problem that sensitivity is insufficient and accurate position information cannot be obtained, and sufficient driving support cannot be performed.

Patent No. 5687231

An object of the present invention is to provide a coated glass article that maintains the high sensitivity of an infrared camera while maintaining infrared absorption performance.

The glass article of the present invention comprises a glass plate having a plate thickness of 2.8 to 5.5 mm,
A glass article provided with a coating provided on one main surface of the glass plate,
The coating contains an infrared absorber,
The glass article has an average transmittance of 18 to 30% at a wavelength of 1000 nm and an average transmittance of 25 to 40% at a wavelength of 1500 nm.

According to the embodiment of the present invention, it is possible to provide a coated glass article that maintains the high sensitivity of an infrared camera while maintaining infrared absorption performance.

  Embodiments of the present invention will be described below.

The form of the glass article of the present invention is a glass plate having a plate thickness of 2.8 to 5.5 mm,
A glass article provided with a coating provided on one main surface of the glass plate,
The coating contains an infrared absorber,
The glass article has an average transmittance of 18 to 30% at a wavelength of 1000 nm and an average transmittance of 25 to 40% at a wavelength of 1500 nm.

The glass article of this embodiment is provided with a film having infrared absorption performance on a glass plate. The glass plate is made of, for example, alkali-free glass, soda lime glass, aluminosilicate glass, or the like, and may be strengthened. Regardless of the strengthening means, physical strengthening or chemical strengthening may be used. The thickness of the glass plate is preferably 2.8 to 5.5 mm, and more preferably 3.0 to 5.0 mm.
If the glass plate is thinner than 2.8 mm, it is possible to maintain high sensitivity of the infrared camera when a coating is provided on the glass plate, but it is difficult to obtain sufficient infrared absorption performance. There is a possibility. If the glass plate is thicker than 5.5 mm, it is possible to maintain high sensitivity of the infrared camera when a coating is provided on the glass plate, but sufficient visible light transmittance can be obtained. Can be difficult.

The film formed on the glass plate is a method of curing after applying the liquid composition to the glass substrate,
It is formed by a method such as attaching a sheet-like material to a glass substrate. Various properties are required for the coating, and various functional additives are often added.

Since the film of the present invention is required to have an infrared absorbing ability, an infrared absorber is contained in the film. When a liquid composition is applied to a glass substrate and then cured to form a film, the infrared absorber must be present in a uniformly dissolved or dispersed state in the liquid composition in order to obtain a homogeneous film. Is done.

If the infrared transmittance of 1500 nm is increased as compared with the conventional glass article, the infrared transmittance of the glass article is increased. 1500nm for high sensitivity infrared camera
It is indispensable to increase the infrared transmittance. Therefore, by reducing the infrared transmittance of 1000 nm, which has almost no effect on the sensitivity of the infrared camera, it is possible to suppress the infrared transmittance as a glass article from increasing compared to the conventional glass article, and the infrared camera. Is functioning with high sensitivity.

The transmittance | permeability in wavelength 1000nm of the infrared rays absorption glass article of this embodiment is 18-30.
% Is preferred. When the transmittance at a wavelength of 1000 nm is 18 to 30%, sufficient infrared absorption ability can be obtained, and the temperature inside the vehicle can be prevented from rising excessively. Wavelength 10
When the transmittance at 00 nm is less than 18%, sufficient infrared absorption ability can be obtained, but the visible light transmittance (Tv) [%] is also relatively lowered, so that it is difficult to maintain high visibility. there is a possibility. Further, if the transmittance at a wavelength of 1000 nm is higher than 30%, there is a possibility that sufficient infrared absorbing ability cannot be obtained.
Furthermore, the transmittance | permeability in wavelength 1500nm of the glass plate with a film used for this invention is 25-25.
It is preferably 40%. When the transmittance at a wavelength of 1500 nm is 25 to 40%, when an infrared camera is used, sufficient infrared transmission can be obtained to maintain high sensitivity, and accurate position information can be obtained. If the transmittance at a wavelength of 1500 nm is less than 25%, it may be difficult to maintain high sensitivity when an infrared camera is used. Further, if the transmittance at a wavelength of 1500 nm is higher than 40%, there is a possibility that sufficient infrared absorbing ability cannot be obtained.

The infrared absorber contained in the coating is selected from tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and composite tungsten oxide. Only one type may be used, or two or more types may be mixed and used. In the present invention, the infrared absorber is used in the form of fine particles.

The content of the infrared absorbing agent in the coating containing the infrared absorbing agent is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, and still more preferably 0.3 to 10% by mass in the coating. When the content of the infrared absorbing agent is 0.1 to 30% by mass in the coating film, sufficient infrared absorbing ability is obtained.

When the film is required to absorb ultraviolet rays, an ultraviolet absorber is contained in the film. When a liquid composition is applied to a glass substrate and then cured to form a coating, the ultraviolet absorber must be present in a uniformly dissolved or dispersed state in the liquid composition in order to obtain a homogeneous film. Is done.

The visible light transmittance (Tv) [%] of the glass plate of the glass article of this embodiment is 72 [%] or more. By setting the visible light transmittance (Tv) [%] to 72 [%] or higher, high visibility can be achieved even when a film having a high infrared transmittance at a specific wavelength is applied while maintaining infrared absorption performance. Can be maintained.

The transmittance of the coated glass plate used in the present invention at a wavelength of 380 nm is preferably 2.
0% or less, More preferably, it is 1.8% or less, More preferably, it is 1.5% or less.
When the transmittance at a wavelength of 380 nm is 2.0% or less, high ultraviolet absorption ability is obtained.

The film thickness of the coating of the present invention is 1 to 10 μm, more preferably 2 to 8 μm, and more preferably 3 to 7 μm. When the film thickness is less than 1 μm, the effect of infrared absorption may be insufficient, and when the film thickness exceeds 10 μm, cracks may occur.

(Infrared absorbing glass article manufacturing method)
The method for producing an infrared-absorbing glass article according to an embodiment of the present invention includes a step of applying a liquid composition containing an infrared absorber on a glass plate, and a transparent substrate coated with the liquid composition containing the infrared absorber. And a heat treatment step. The manufacturing method may have other steps as necessary. By the heat treatment, the liquid composition containing the infrared absorbing agent is cured, and a film having infrared absorbing ability is formed.

As a method for applying the composition containing the infrared absorber, a general application method such as spin coating, dip coating, spray coating, flow coating, or die coating can be used. The flow coat can be particularly preferably used in the case of a glass plate having a curved shape.

Then, the glass plate which apply | coated the liquid composition containing an infrared absorber is heated, and the film which has infrared absorption ability is formed. An electric furnace, a gas furnace, an infrared heating furnace, or the like can be used for heating. The temperature and time of the heat treatment can be adjusted as appropriate, for example, 70 to 300.
It is in the range of ° C. The heating time is, for example, 1 to 180 minutes.

Examples of the film formed on the glass plate include a film made of a thermoplastic resin, a film made of a cured product of a curable resin, a silicon oxide film by a sol-gel method, and the like.

(Liquid composition containing infrared absorber)
The liquid composition containing the infrared absorber for forming the coating film according to the embodiment of the present invention will be described below. The liquid composition used in the present invention comprises at least one matrix component,
1 type infrared absorber.

The liquid composition used in the present invention includes additives such as an acid catalyst, an ultraviolet absorber, a dispersant, a chelating agent, a liquid medium, an antifoaming agent, a leveling agent, an adhesion imparting agent, a dye, a pigment, and a filler. It may be included.

[Matrix component]
The matrix component of the liquid composition used in the present invention is a main component for film formation. Examples of the matrix component include a thermoplastic resin, a curable resin, and a silicon oxide matrix component.

The silicon oxide matrix component may be composed of only a hydrolyzable silane compound, but may further contain a flexible component and silicon oxide fine particles in addition to the hydrolyzable silane compound.

In the present invention, the hydrolyzable silane compound undergoes hydrolysis (co) condensation to obtain a film. Therefore, it is required that water, an acid catalyst, etc. are added to the liquid composition.

The hydrolyzable silane compound is preferably composed only of a tetrafunctional hydrolyzable silane compound, or a tetrafunctional hydrolyzable silane compound, a bifunctional hydrolyzable silane compound and / or a trifunctional hydrolyzable compound. It is composed of a decomposable silane compound. More preferably, it is composed only of a tetrafunctional hydrolyzable silane compound.

Examples of the tetrafunctional hydrolyzable silane compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, and tetra-sec-butoxysilane. In the present invention, tetraethoxysilane, tetramethoxysilane or the like is preferably used. These may be used alone or in combination of two or more.

Examples of the trifunctional hydrolyzable silane compound include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and phenyltrimethoxysilane. These may be used alone or in combination of two or more.

Examples of the bifunctional hydrolyzable silane compound include dimethyldimethoxysilane and dimethyldiethoxysilane. These may be used alone or in combination of two or more.

A flexible component can contribute to suppression of the crack generation in a film. In particular, when the silicon oxide matrix component is composed only of a tetrafunctional hydrolyzable silane compound, the coating may not be sufficiently flexible. If the liquid composition contains a flexible component together with the tetrafunctional hydrolyzable silane compound, a film excellent in both mechanical strength and crack resistance can be easily produced.

In the present invention, among the above flexible components, epoxy resins, particularly polyepoxides, PEG, glycerin, and the like are preferable from the viewpoint that sufficient flexibility can be imparted to the coating film while maintaining mechanical strength. In addition, the above epoxy resins, especially polyepoxides, PEG, glycerin, and the like absorb infrared rays and ultraviolet rays while ensuring colorless transparency of the coating in addition to the function of preventing the occurrence of cracks due to light irradiation over a long period of time. It also has a function of suppressing a decrease in various functions such as the above. In the present invention, polyepoxides are particularly preferable among these.

The content of the matrix component in the liquid composition containing the infrared absorber is 60% in the composition.
-95 mass% is preferable, 70-90 mass% is more preferable, 80-90 mass% is further more preferable. In addition, content of a matrix component is solid content conversion content. In the present invention, the content in terms of solid content of a component refers to the mass of the residue excluding volatile components such as water.

[Acid catalyst]

In order for the hydrolyzable silane compound to undergo hydrolytic (co) condensation, an acid catalyst is added to the liquid composition.

Examples of the acid catalyst include inorganic acids such as nitric acid and hydrochloric acid, carboxylic acids such as formic acid, acetic acid, propionic acid, maleic acid and phthalic acid, and sulfonic acids such as metasulfonic acid. More preferred are carboxylic acids.

[Ultraviolet absorber]
The liquid composition may contain an ultraviolet absorber in order to impart ultraviolet absorbing ability. As the ultraviolet absorber, a benzophenone-based ultraviolet absorber, specifically, 2,4-dihydroxybenzophenone, 2,2 ′, 3 (or any of 4, 5, 6) -trihydroxybenzophenone, 2,2 ′ , 4,4′-tetrahydroxybenzophenone, 2,4-dihydroxy-2 ′, 4′-dimethoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and the like. Among these, 2,2 ', 4,4'- is preferable.
Tetrahydroxybenzophenone is used.

0.01-15 mass% in a liquid composition is preferable, as for content of the ultraviolet absorber in a liquid composition, 0.1-10 mass% is more preferable, and 1-5 mass% is further more preferable. When the content of the ultraviolet absorber is 0.01 to 15% by mass in the liquid composition, sufficient ultraviolet absorbing ability is obtained.

[Dispersant]
The dispersant is a component used for the purpose of dispersing the fine particles constituting the infrared absorber in the liquid composition with dispersion stability. Further, the dispersant has an action of suppressing the chelate bond between the fine particles constituting the infrared absorber existing together in the liquid composition and the ultraviolet absorber.
In addition, in the liquid composition of this invention, it cannot be said that the effect which suppresses this chelate bond alone is enough, and it can become sufficient by combined use with the below-mentioned chelating agent.

Here, in this specification, the dispersant is a dispersion medium (a part of the liquid medium) from at least the molecule, the surface adsorbing the fine particles constituting the infrared absorber, the adsorbing site, and the adsorbing site after adsorbing to the fine particle. The dispersion stability of the fine particles of the infrared absorber is increased by having a portion that stably disperses the fine particles in the liquid composition due to the repulsion of electric charges and steric hindrance. It is a general term for compounds having the function of The dispersing agent and the chelating agent described later are different in that the chelating agent is adsorbed on the fine particles of the infrared absorbing agent but does not have a function of increasing the dispersion stability.

As the dispersant, commercially available dispersants for solid fine particles can be used. Specifically, as a dispersant having an acid value or an amine value, DISPERBYK-190 (molecular weight: 2200, acid value: 10 mgKOH / g, solid content: 40 mass by the product name of Big Chemie Japan Co., Ltd., which is a styrene-based dispersant. % Aqueous solution), DISPERBYK-180 (molecular weight: 2000, acid value: 95 mgKOH / g, amine value 95 mgKOH / g, solid content 10)
0% by mass) DISPERBYK-185 (molecular weight: 1500, amine value: 18 mgKOH /
g, solid content 100% by mass), and the like.

The content of the dispersant in the liquid composition containing the infrared absorber is 0.01 to 10 in the composition.
% By mass is preferable, 0.1 to 5% by mass is more preferable, and 1 to 3% by mass is more preferable.
When the content of the dispersant is 0.01 to 10% by mass in the composition, the solid fine particles can be sufficiently dispersed in the composition.

[Chelating agent]
The chelating agent acts on the fine particles of the infrared absorbent together with the dispersant, and has an action of suppressing the chelating bond of the ultraviolet absorbent to the fine particles of the infrared absorbent.

In the present specification, the chelating agent is a compound that can be coordinated to a plurality of locations on the surface of the fine particles of the infrared absorbing agent with one molecule, and the steric hindrance after adsorption to the fine particles due to the molecular structure is small, This is a general term for compounds that do not have the function of increasing the dispersion stability of the fine particles of the infrared absorber.

In the present invention, the dispersant has a portion that adsorbs to the surface of the fine particles of the infrared absorber and a portion that extends into the dispersion medium (becomes a part of the liquid medium) and ensures dispersion stability, An appropriate amount for ensuring the dispersion stability of the fine particles of the infrared absorber in the liquid composition is contained.
Usually, an appropriate amount of such a dispersant does not necessarily sufficiently cover the surface of the fine particles of the infrared absorber,
In addition, the amount is not sufficient to suppress the chelate bond of the ultraviolet absorber. Therefore, in the present invention, by adding a chelating agent to the liquid composition, the surface of the infrared absorbent fine particles are sufficiently covered together with the dispersant, and the chelating bond of the ultraviolet absorbent to the infrared absorbent fine particles is achieved. It was assumed that it could be sufficiently suppressed.

In the present invention, a commercially available product can be used as the chelating agent. As a commercial item, for example, non-pole PMA-50W (trade name, manufactured by NOF Corporation, molecular weight: polymaleic acid,
1,200, an aqueous solution having a solid content of 40 to 48% by mass) and the like as a polyacrylic acid, Aquaric HL (trade name, manufactured by Nippon Shokubai, molecular weight: 10,000, an aqueous solution having a solid content of 45.5% by mass)
Etc.

The chelating agent used in the present invention is a chelating agent capable of forming a complex with the infrared absorbing agent, and the formed complex does not substantially absorb light with a visible light wavelength,
And the molecular weight is 1,000-100,000. The molecular weight is 1,500-100,
000 is preferable, and 2,000 to 100,000 is more preferable. If the molecular weight of the chelating agent is within the above range, it can be sufficiently adsorbed and coordinated on the surface of the infrared absorbent fine particles together with the dispersant, and the ultraviolet absorbent can be sufficiently inhibited from chelating with the fine particles of the infrared absorbent.

Here, “substantially no absorption” means, for example, a liquid composition in which 50 parts by mass of a chelating agent is added to 100 parts by mass of the infrared absorber, and 0.7 g of the infrared absorber on the substrate. / M
The film is formed on the substrate so as to be deposited in an amount of 2, and the obtained coated substrate is JIS K71.
05 (1981) This means that the difference between the YI (Yellow Index) value and the YI measured for only the substrate is 2.0 or less.

[Liquid medium]
A liquid medium is used to dissolve and disperse the entire solid content in the liquid composition of the present invention.

Examples of the liquid medium used in the present invention include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, methanol, ethanol, 1-propanol, 2-
Examples thereof include alcohols such as propanol, carboxylic acids such as acetic acid, nitriles such as acetonitrile, and water. These may be used alone or in combination of two or more.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following description. Examples 1 to 11 described below are examples, and examples 12 to
15 is a comparative example.

<Preparation Example of Infrared Absorber Dispersion>
ITO ultrafine particles as an infrared absorber (Mitsubishi Materials Corporation, average primary particle size 20 nm
11.9 g of an average dispersed particle size of 55 nm), 3.0 g of DISPERBYK-190 (manufactured by Big Chemie Japan, acid value 10 mg KOH / g, 40 mass% aqueous solution of a dispersant having a molecular weight of 2,200), Solmix AP- 24 of a mixed solvent of 1 (produced by Nippon Alcohol Sales Co., Ltd., ethanol: 2-propanol: methanol = 85.5: 13.4: 1.1 (mass ratio)).
2 g was dispersed for 48 hours using a ball mill, and then Solmix AP-1 was further added to dilute the ITO solid content concentration to 20% by mass to obtain an infrared absorbent dispersion.

<Preparation example of UV absorber solution>
2,2 ′, 4,4′-tetrahydroxybenzophenone (BASF) 49.2 g,
3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) 123.2 g, benzyltriethylammonium chloride (Pure Chemical Co., Ltd.) 0.8 g, butyl acetate (Pure Chemical Co., Ltd.) 1
00 g was charged and heated to 60 ° C. with stirring, dissolved, heated to 120 ° C. and reacted for 4 hours to obtain a UV absorber solution having a solid content concentration of 63% by mass.

(Example 1)
4.5 g of infrared absorbent dispersion, 45.3 g of Solmix AP-1, 18.1 of pure water
g, 11.0 g of tetraethoxysilane, 1.1 g of SR-SEP (Sakamoto Yakuhin Kogyo Co., Ltd.)
, 0.3 g of non-pole PMA-50W (manufactured by NOF Corporation), 11.5 g of 90% acetic acid, 0.1 g of polyether-modified polydimethylsiloxane (Big Chemie Japan Co., Ltd.), 12.6 g of UV absorber solution And stirred at 50 ° C. for 2 hours to obtain a liquid composition 1.

Thereafter, the surface is polished and cleaned with cerium oxide as a substrate, and a dry glass substrate made of soda lime glass (plate thickness: 5 mm, Tv: 74.3%, T380: 48.
7%, T1000: 19.5%, T1500: 36.1%), and the liquid composition 1 was applied to the surface of the glass substrate by spin coating. Then in an electric furnace at 200 ° C
The glass article which hold | maintained for 5 minutes and has an infrared rays absorption layer was obtained.

(Example 2)
In Example 1, a glass article having an infrared absorbing layer was obtained in the same manner as in Example 1 except that the addition amount of the infrared absorbent dispersion was changed to 2.5 g.

(Example 3)
In Example 1, a glass article having an infrared absorbing layer was obtained in the same manner as in Example 1 except that the addition amount of the infrared absorbent dispersion was changed to 0.5 g.

(Example 4)
6.0 g of infrared absorbent dispersion, 45.3 g of Solmix AP-1, 18.1 of pure water
g, 11.0 g of tetraethoxysilane, 1.1 g of SR-SEP (Sakamoto Yakuhin Kogyo Co., Ltd.)
, 0.3 g of non-pole PMA-50W (manufactured by NOF Corporation), 11.5 g of 90% acetic acid, 0.1 g of polyether-modified polydimethylsiloxane (Big Chemie Japan Co., Ltd.), 12.6 g of UV absorber solution And stirred at 50 ° C. for 2 hours to obtain a liquid composition 4.

Thereafter, the surface is polished and cleaned with cerium oxide as a substrate, and a dry glass substrate made of soda lime glass (plate thickness: 4 mm, Tv: 74.8%, T380: 32.
7%, T1000: 27.3%, T1500: 45.3%), and the liquid composition 4 was applied to the surface of the glass substrate by spin coating. Then in an electric furnace at 200 ° C
The glass article which hold | maintained for 5 minutes and has an infrared rays absorption layer was obtained.

(Example 5)
In Example 4, the glass article which has an infrared rays absorption layer was obtained like Example 4 except having changed the addition amount of the infrared absorber dispersion into 4.5g.

(Example 6)
In Example 4, a glass article having an infrared absorbing layer was obtained in the same manner as in Example 4 except that the addition amount of the infrared absorbent dispersion was changed to 3.0 g.

(Example 7)
In Example 4, the glass article which has an infrared rays absorption layer was obtained like Example 4 except having changed the addition amount of the infrared absorber dispersion into 2.0g.

(Example 8)
6.5 g of infrared absorbent dispersion, 45.3 g of Solmix AP-1, 18.1 of pure water
g, 11.0 g of tetraethoxysilane, 1.1 g of SR-SEP (Sakamoto Yakuhin Kogyo Co., Ltd.)
, 0.3 g of non-pole PMA-50W (manufactured by NOF Corporation), 11.5 g of 90% acetic acid, 0.1 g of polyether-modified polydimethylsiloxane (Big Chemie Japan Co., Ltd.), 12.6 g of UV absorber solution And stirred at 50 ° C. for 2 hours to obtain a liquid composition 8.

Thereafter, the surface is polished and cleaned with cerium oxide as a substrate, and a dry glass substrate made of soda lime glass (plate thickness: 3.2 mm, Tv: 74.9%, T380: 3
3.2%, T1000: 28.5%, T1500: 46.2%), and the liquid composition 8 was applied to the surface of the glass substrate by spin coating. Subsequently, it hold | maintained for 25 minutes with the 200 degreeC electric furnace, and obtained the glass article which has an infrared rays absorption layer.

(Example 9)
In Example 8, a glass article having an infrared absorbing layer was obtained in the same manner as in Example 8 except that the addition amount of the infrared absorbent dispersion was changed to 5.0 g.

(Example 10)
In Example 8, the glass article which has an infrared rays absorption layer was obtained like Example 8 except having changed the addition amount of the infrared absorber dispersion into 3.5g.

(Example 11)
In Example 8, the glass article which has an infrared rays absorption layer was obtained like Example 8 except having changed the addition amount of the infrared absorber dispersion into 2.0g.

(Example 12)
In Example 4, a glass article having an infrared absorbing layer was obtained in the same manner as in Example 4 except that the addition amount of the infrared absorbent dispersion was changed to 7.0 g.

(Example 13)
In Example 4, a glass article having an infrared absorbing layer was obtained in the same manner as in Example 4 except that the addition amount of the infrared absorbent dispersion was changed to 0.5 g.

(Example 14)
7.0 g of infrared absorbent dispersion, 45.3 g of Solmix AP-1, 18.1 of pure water
g, 11.0 g of tetraethoxysilane, 1.1 g of SR-SEP (Sakamoto Yakuhin Kogyo Co., Ltd.)
, 0.3 g of non-pole PMA-50W (manufactured by NOF Corporation), 11.5 g of 90% acetic acid, 0.1 g of polyether-modified polydimethylsiloxane (Big Chemie Japan Co., Ltd.), 12.6 g of UV absorber solution And stirred at 50 ° C. for 2 hours to obtain a liquid composition 14.

Thereafter, the surface is polished and cleaned with cerium oxide as a substrate, and a dry glass substrate made of soda-lime glass (plate thickness: 2.8 mm, Tv: 76.1%, T380: 3
5.8%, T1000: 31.1%, T1500: 48.9%), and the liquid composition 14 was applied to the surface of the glass substrate by spin coating. Subsequently, it hold | maintained for 25 minutes with the 200 degreeC electric furnace, and obtained the glass article which has an infrared rays absorption layer.

(Example 15)
In Example 14, the glass article which has an infrared rays absorption layer was obtained like Example 14 except having changed the addition amount of the infrared absorber dispersion into 2.5g.

[Film thickness]
A cross-sectional image of a glass article having an infrared absorbing layer was scanned with a scanning electron microscope (Hitachi, S43).
00), and the film thickness of the infrared absorption layer was measured.

[Transmittance measurement]
The spectrophotometer (manufactured by Hitachi, Ltd .: U-41)
00), and in accordance with ISO-9050 (1990), visible light transmittance (Tv [%]) of the glass plate, wavelengths of the coated glass plate of 380 nm, 1000 nm, 1500 n
The transmittance in m, T380 [%], T1000 [%], and T1500 [%] were calculated, respectively.

  Table 1 shows the measurement results of the thickness and transmittance of the glass plates of Examples 1 to 15.

Examples 1 to 11 have an average transmittance of 18 to 30% at a wavelength of 1000 nm and a wavelength of 1500
The average transmittance at nm was 25 to 40%, and it was possible to prevent the interior of the vehicle from getting hot while improving the sensitivity of the infrared camera. In Example 12, since the average transmittance at a wavelength of 1500 nm was 22.5%, the sensitivity of the infrared camera was not sufficient.
Since the average transmittance at 00 nm was 43.6%, it was not possible to sufficiently prevent the interior of the vehicle from getting hot. In Example 14, the average transmittance at a wavelength of 1000 nm was 30.6%, so In Example 15, the wavelength of 1000 cannot be sufficiently prevented from becoming hot.
Since the average transmittance at nm was 30.9% and the average transmittance at a wavelength of 1500 nm was 40.1%, it was not possible to sufficiently prevent the inside of the vehicle from getting hot.

The glass plate with a film of the present invention can be applied to a door glass plate for automobiles and the like.

Claims (6)

A glass plate having a plate thickness of 2.8 to 5.5 mm;
A glass article provided with a coating provided on one main surface of the glass plate,
The coating contains an infrared absorber,
A glass article having an average transmittance of 18 to 30% at a wavelength of 1000 nm and an average transmittance of 25 to 40% at a wavelength of 1500 nm. The glass article according to claim 1, wherein the infrared absorber contains at least one selected from the group consisting of tin-doped indium oxide, antimony-doped tin oxide, and composite tungsten oxide. The glass article according to claim 2, wherein the content of the infrared absorbent in the coating is 0.1 to 30% by mass. The glass article according to claim 1, wherein the coating contains an ultraviolet absorber. The visible light transmittance (Tv) of the glass plate is 72% or more,
The glass article according to claim 1. The transmittance of the glass article at a wavelength of 380 nm is 2.0% or less,
The glass article according to claim 4.