JP2000109345A - Glass product coated with antireflection color film and optical filter for plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass product coated with an antireflection color film which has excellent antireflection performance for visible rays and which arbitrarily controls the color tone of transmitted light and which has high transmittance for visible rays, and to provide an optical filter for a PDP by using the product described above. SOLUTION: This glass product coated with an antireflection color film is produced by forming a high refractive index film on a transparent glass substrate having a refractive index of 1.47 to 1.53, and further forming a low refractive index film on the high refractive index film. The high refractive index film has a refractive index of 1.59 to 2.30 and a thickness of 80 to 140 nm, and contains 0 to 85 wt.% silicon oxide, 10 to 95 wt.% titanium oxide and 5 to 30 wt.% gold fine particles. The low refractive index film has a refractive index smaller by at least 0.20 than that of the high refractive index film, has a film thickness of 70 to 99 nm, and contains 90 to 100 wt.% silicon oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass article coated with an anti-reflection colored film, and more particularly to a glass plate coated with an anti-reflection colored film which reduces visible light reflection and adjusts transmission color tone, and an optical filter using the same.

[0002]

2. Description of the Related Art Antireflection films have conventionally been used for optical parts such as cameras and glasses, or display parts of OA electronic equipment such as display panels and displays. These antireflection films are required to have high transmissivity as well as low reflectivity in order to enhance the visibility or to further enhance the optical characteristics originally provided.

[0003] Many colored films in which noble metal fine particles are doped in an inorganic oxide are known. For example, a glass with a colored film can be obtained by doping gold particles in a silica-titania film, and depending on the amount of silica and titania in the film, red, magenta, blue,
It is disclosed that colors such as turquoise and green can be obtained. [For example, (a) H. Kozuka, Control of Optical pro
perties of gel-derived oxide coating films containi
ng finemetal particles (Control of optical properties of oxide coating film containing metal fine particles derived from gel), J. Sol-Gel Sci. Te
ch., 2,741-744 (1994), and JP-A-6-19189.
6]

Further, by doping gold fine particles in a silica film or a silica-titania film, the visible light reflectance (light irradiation from the film surface side) is 5 to 7%, and the red, reddish purple, green gray and gray are obtained. A colored film-coated glass article having a thickness of 80 to 140 nm which is colored is disclosed ((b)).
JP-A-9-295834).

On the other hand, a plasma display panel (PD)
P) has recently been put to practical use as a large-screen wall-mounted television, and has been actively developed for further popularization. This P
It is known to provide an optical filter that has a multilayer antireflection film layer for preventing reflection of external light and an electromagnetic wave shielding layer on the front surface of the DP and corrects the emission color of the PDP.
For example, by mixing a colored transparent substrate (made of acrylic resin or polycarbonate resin, which absorbs the excess red component emitted by PDP into the resin, it prevents the color tone that should be blue from appearing purple. ) Is bonded with a transparent adhesive on one surface of an antireflection film (a film obtained by stacking a plurality of films of materials having different refractive indices), and the other surface of the transparent substrate is provided with (1) an electromagnetic wave and a near-infrared region. (For example, a film obtained by sputtering silver-inorganic oxide fine particles on the surface of a PET film), and (2) an anti-interference fringe film (for example, PDP in which fine irregularities are formed on the outer surface of a transparent film) Are bonded in that order with a transparent pressure-sensitive adhesive.
(For example, (c) JP-A-9-306366)

[0006]

The colored film (a) doped with the noble metal fine particles can control the color tone to some extent, but has little antireflection performance. In addition, a statement about the reflectance (b)
Also, there was a problem that the value of the visible light reflectance was not so different from that of the untreated transparent substrate, and the transmittance was significantly reduced.

On the other hand, with respect to the optical filter used in the PDP, in the above (c), there is a problem that the pigment is mixed in the resin plate and the antireflection film is attached to the surface thereof, so that the production cost increases.

The present invention solves the above-mentioned problems of the prior art, and has an excellent antireflection performance for visible light, can freely control the color tone of transmitted light, and has a high visible light transmittance. An object of the present invention is to provide a coated glass article and to provide an optical filter for a PDP using the same.

[0009]

According to the present invention, an antireflection film composed of two layers having different refractive indices is formed on a transparent glass substrate, and at least one of these layers is used as a selective absorption film to provide a coloring function. An anti-reflection colored film is obtained by giving.

That is, the present invention has a refractive index of 1.47 to
On a 1.53 transparent glass substrate, having a refractive index of 1.59 to 2.30 and a film thickness of 80 to 140 nm, 0 to 85% silicon oxide, 10 to 95% A high refractive index film containing titanium oxide and 5 to 30% of fine gold particles is formed, and 1.35-1.
A refractive index within a range of 58 and at least 0.20 smaller than the refractive index of the high refractive index film;
An anti-reflection colored film-coated glass article having a low refractive index film having a thickness of 90 nm and containing 90 to 100% by weight of a silicon oxide expressed in% by weight. Has a refractive index in the range of 1.59 to 2.30 and at least 0.20 smaller than the refractive index of the high refractive index film, and a film thickness of 80 to 140 nm, and
0 to 89% of silicon oxide, 11 to 100%
A high refractive index film containing titanium oxide is formed, and a refractive index of 1.35 to 1.58, 70 to 99 is formed on the high refractive index film.
An anti-reflective colored film-coated glass article having a thickness of 70 nm and comprising a low refractive index film containing 70 to 95% by weight of silicon oxide and 4 to 30% of fine gold particles in weight%. .

The components of the high refractive index film according to the present invention will be described below. Although silicon oxide is not an essential component, it is effective for adjusting the refractive index of the film, and when its content is low, the refractive index of the colored film increases and the film exhibits a bluish green color. Conversely, when the content is large, the refractive index of the colored film becomes low, and the film exhibits reddish purple. If the silicon oxide content is too high, the substrate is deformed by a large shrinkage of the film in the film heating step, so that the silicon oxide content is 0 to 85% by weight in terms of SiO ₂ , preferably 0-70% by weight
It is.

[0012] Titanium oxide is necessary for film formation and to increase the refractive index of the colored film. When the content is low, the refractive index of the colored film is reduced, and the film exhibits reddish purple. When the content is large, the refractive index of the colored film increases, and the film exhibits blue-green color. If the content of the titanium oxide is too low, the film formability and transparency of the film are reduced,
Its content is 10 to 95% by weight in terms of TiO _2, preferably 20 to 90 wt%, more preferably from 25 to 85 wt%.

[0013] Gold is necessary as coloring fine particles to impart color to the high refractive index film. If the content is too low, sufficient coloring cannot be obtained, and if it is too high, the durability of the film will be poor. The gold particles are reduced or surplus gold fine particles come out of the film and do not contribute to coloring. Therefore, the content of the fine gold particles is 5 to 3
0 wt%, preferably 5 to 25 wt%, more preferably 8 to 23 wt%.

If the thickness d ₁ (physical film thickness) of the high refractive index film is too small, the antireflection effect is reduced and the coloring effect is reduced. Conversely, if the thickness is too large, the antireflection effect will be low, and the film strength will be reduced due to cracks, so the thickness is 80 to 140 nm, preferably 85 to 125 nm.
nm, more preferably 89 to 125 nm.
Then the refractive index n ₁ and the anti-reflection effect is too low of a high refractive index film can not be obtained sufficiently, a 1.59 to 2.30, preferably 1.65 to 2.23, more preferably 1.70 to 2.20. The refractive index of this high-refractive-index film was 550 nm for a film containing silicon oxide and titanium oxide in a state not containing gold fine particles.
Defined as a value at wavelength. The optical thickness of the high refractive index film (n
₁ d ₁ ) preferably has a value of の of one of wavelengths in a visible light range (380 to 680 nm) in order to reduce the visible light reflectance. The optical thickness is preferably in the range of 95 to 170 nm. However, within this range, the reflected color tends to be reddish,
Since the red reflection color is often not preferred, it is preferable to select an optical film thickness of 155 to 230 nm slightly larger than the above range in order to make the reflection color bluish.

The low refractive index film of the present invention will be described below. Silicon oxide is necessary for forming the film and for lowering the refractive index of the low-refractive-index film. The content of silicon oxide is 90 to 100% by weight in terms of SiO ₂ ,
Preferably it is 92 to 100% by weight, more preferably 95 to 100% by weight.

If the thickness d ₂ (physical film thickness) of the low refractive index film is too small, the antireflection effect is reduced. On the other hand, if the thickness is too large, cracks occur and the film strength is reduced.
９９99 nm, preferably 75-95 nm,
More preferably, it is 77 to 93 nm. And because too high antireflection effect is the refractive index of the low refractive index film is not sufficiently obtained, the refractive index n ₂ of the low refractive index film is 1.35 to 1.58
And at least 0.20 smaller than the refractive index of the high refractive index film, preferably from 1.36 to
1.53, and more preferably 1.37 to 1.49. Note that the refractive index of this low refractive index film is defined as a value at a wavelength of 550 nm, and the refractive index of the low refractive index film when gold particles are contained in the low refractive index film contains gold particles as described later. It is defined as a value for a film containing silicon oxide in a state where no silicon oxide is contained. The optical thickness (n ₂ d ₂ ) of the low refractive index film may have a value that is a quarter of any wavelength in the visible light range (380 to 680 nm, preferably 420 to 600 nm having high visibility). It is preferable to reduce the visible light reflectance, and specifically, the optical film thickness of the low refractive index film is preferably in the range of 105 to 150 nm.

In the above, the case where the gold fine particles are contained in the high refractive index film has been described. However, the gold fine particles may be contained in the low refractive index film instead of being contained in the high refractive index film. In this case, each component of the high refractive index film that does not contain the fine gold particles will be described below.

Although silicon oxide is not an essential component, it is effective for adjusting the refractive index of the film. When the silicon oxide content is too large, since the substrate due to the large shrinkage of the film in the heating step of the membrane deforms, the content of silicon oxide, SiO ₂
0 to 89% by weight, preferably 10 to 7%
The content is 5% by weight, more preferably 20 to 70% by weight.

Titanium oxide is necessary for forming the film and for increasing the refractive index of the colored film. If the content of titanium oxide is too low, the effect of preventing reflection becomes difficult to obtain, since the film forming property and transparency of the film is lowered, and the content thereof in terms of TiO ₂ eleven to one hundred wt% , Preferably 20 to 95% by weight, more preferably 30 to 85% by weight.

The low refractive index film containing the fine gold particles will be described below. Silicon oxide is necessary for forming the film and for lowering the refractive index of the low refractive index film, and the content of silicon oxide is 70 to 70 in terms of SiO _2.
It is 96% by weight, preferably 72-96% by weight, and more preferably 75-96% by weight.

The fine gold particles in the low-refractive-index film are necessary as coloring fine particles to impart color to the low-refractive-index film. If the content is too low, sufficient coloring cannot be obtained. If the amount is too large, the durability of the film is reduced, or excessive gold fine particles come out of the film and do not contribute to coloring. Therefore, the content of the gold fine particles is 4 to 30% by weight, preferably 4 to 30% by weight.
-25% by weight, more preferably 4-23% by weight.

The case where gold fine particles are contained in the high refractive index film and the case where gold fine particles are contained in the low refractive index film have been described above. However, other than these cases, that is, gold fine particles may be contained in both the high refractive index film and the low refractive index film. In this case, the high refractive index film is formed by replacing silicon oxide with Si for the same reason as in the case of the above high refractive index film.
O ₂ in terms of 0 to 89 wt%, preferably from 10 to 75
Wt%, more preferably 20 to 65 wt%, titanium oxide, 10-100% in terms of TiO _2, preferably 20 to 95%, more preferably 30 to 85 wt%, and from 0 to gold particles 30% by weight, respectively. The low-refractive-index film, for the same reason as that in the low refractive index film, a silicon oxide, in terms of SiO ₂ 70 to 10
0% by weight, preferably 72 to 96% by weight, more preferably 75 to 96% by weight, and 0 to 30% by weight of fine gold particles. Here, the sum of the content of the fine gold particles in the high refractive index film and the content of the fine gold particles in the low refractive index film is 4 to 30% by weight, preferably 4 to 25% by weight, and more preferably 8 to 20% by weight. %.

The high-refractive-index film containing or not containing the above-mentioned gold fine particles is composed of silicon oxide, titanium oxide, and other components such as zirconium oxide, cerium oxide, zinc oxide, tantalum oxide, cobalt oxide, and oxide. Chromium, copper oxide, manganese oxide, nickel oxide, iron oxide, and fine gold particles (when the high refractive index film does not require the presence of fine gold particles) and the like, ZrO ₂ , CeO ₂ , ZnO, Ta ₂ O ₅ , CoO, C
In terms of rO, CuO, MnO, NiO, Fe ₂ O ₃ and Au, a small amount of these totals, for example, 10% by weight or less, may be contained. Here, the total of the content of Au fine particles in the high refractive index film and the content of Au fine particles in the low refractive index film preferably does not exceed 30% by weight.

Similarly, the low-refractive-index film containing or not containing the above-mentioned gold fine particles contains, in addition to silicon oxide, other components such as titanium oxide, zirconium oxide, cerium oxide, zinc oxide, tantalum oxide, Cobalt oxide, chromium oxide, copper oxide, manganese oxide, nickel oxide, iron oxide, and fine gold particles (when the low refractive index film does not require the presence of fine gold particles) and the like, TiO ₂ , ZrO ₂ , CeO ₂ , Zn
O, Ta ₂ O ₅ , CoO, CrO, CuO, MnO, Ni
In terms of O, Fe ₂ O ₃ and Au, the total of these may be contained in a small amount, for example, 10% by weight or less. Here, the sum of the content of Au fine particles in the low refractive index film and the content of Au fine particles in the high refractive index film preferably does not exceed 30% by weight.

The method for forming the high refractive index film and the low refractive index film of the present invention includes a sol-gel method, a sputtering method, and a CV method.
Although it can be formed by the D method or the like, the sol-gel method is more preferable in terms of cost. For the coating by the sol-gel method, a spin coating method, a dip coating method, a flow coating method, a meniscus coating method, a roll coating method, a gravure coating method, a flexographic printing method, a screen printing method and the like are used.

When the high refractive index film and the low refractive index film of the present invention are formed by a sol-gel method, for example, to form an optical thin film containing titanium oxide, silicon oxide and fine gold particles,
The coating composition comprises a titanium compound, a silicon compound, a gold material and a solvent, and is obtained by mixing the titanium compound, the silicon compound and the gold material with an organic solvent.

As the titanium compound, titanium alkoxide, titanium alkoxide chloride, titanium chelate and the like are used. As titanium alkoxide, titanium methoxide, titanium ethoxide, titanium n-propoxide,
Examples thereof include titanium isopropoxide, titanium n-butoxide, titanium isobutoxide, titanium methoxypropoxide, titanium stearyl oxide, and titanium 2-ethylhexoxide. Examples of the titanium alkoxide chloride include titanium chloride triisopropoxide, titanium dichloride diethoxide and the like. Titanium chelates include titanium triisopropoxide (2,4-pentanedionate), titanium diisopropoxide (bis-2,4-pentanedionate), titanium allyl acetate triisopropoxide, titanium bis (triethanol Amine) diisopropoxide, titanium di-n-butoxide (bis-2,4-
Pentanedionate) and the like.

As the silicon compound, a compound obtained by mixing silicon alkoxide with a solvent such as alcohol, and promoting hydrolysis and polymerization with an acidic or basic catalyst is used. As the silicon alkoxide, silicon methoxide, silicon ethoxide, or an oligomer thereof is used.
As the acid catalyst, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, trichloroacetic acid, trifluoroacetic acid, phosphoric acid, hydrofluoric acid, formic acid and the like are used. Ammonia, as a basic catalyst,
Amines are used.

As raw materials for the fine gold particles, chloroauric acid tetrahydrate, chloroauric acid trihydrate, sodium chloroaurate dihydrate,
Examples include gold cyanide, potassium gold cyanide, gold diethylacetylacetonate complex, and a gold colloid dispersion solution.

The organic solvent used in the coating liquid composition used for forming the high refractive index film and the low refractive index film depends on the coating method.
Isopropanol, butanol, hexanol, octanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, propylene glycol monomethyl ether, propylene glycol monoethyl glycol, cellosolve acetate, ethylene glycol,
Examples include propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, hexylene glycol, diethylene glycol, tripropylene glycol, polypropylene glycol, diacetone alcohol and the like. As the coating liquid composition, the above-mentioned solvent may be used alone or plurally in order to adjust the viscosity, surface tension and the like of the coating liquid. Also stabilizers, leveling agents,
A small amount of a thickener or the like may be added as needed. The amount of the solvent used depends on the thickness of the high-refractive index film and low-refractive index film finally obtained, and the coating method to be used, but is usually used so that the total solid content falls within the range of 1 to 20%. Is done.

After the above-mentioned coating solution composition is applied by the above-mentioned coating method, it is dried or / and baked by heating at a temperature of 250 ° C. or more. Then, after applying the next coating solution, it is dried and / or 250 ° C. or more. By heating and baking at a temperature, an antireflection colored film-coated glass article is completed. The coating obtained in this way has excellent properties such as transparency, environmental resistance, and scratch resistance, and the process of densification of the high-refractive-index film layer and the low-refractive-index film layer even when they are laminated. In this case, it is possible to suppress film peeling and generation of cracks, which are likely to occur due to the difference in the thermal shrinkage in the above.

The light irradiation method described below can be used in place of the above-described manufacturing method using drying and / or baking by heating at 250 ° C. or more. That is, after applying the coating solution composition by the coating method, performing a step of irradiating the coating film with an electromagnetic wave having a shorter wavelength than visible light, and subsequently applying the next coating solution, the wavelength than visible light Irradiating the coating film with a short electromagnetic wave of
This is a method in which the drying step is repeated. Examples of electromagnetic waves having a wavelength shorter than that of visible light include γ-rays, X-rays, and ultraviolet rays. However, ultraviolet irradiation is preferable from the viewpoint of practicality of the apparatus in consideration of irradiation to a substrate having a large area. As an ultraviolet light source, an excimer lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, or the like is used. Using a high-pressure mercury lamp that efficiently emits light at 254 nm and 303 nm with a main wavelength of 365 nm, 10 mW / cm ² or more, preferably 50 mW / cm ² or more, and more preferably 100 mW / cm ² or more.
It is desirable to irradiate the coating film with an irradiation intensity of W / cm ² or more. Using such an ultraviolet light source, 100 mJ / c
m ² or more, preferably 500 mJ / cm ² or more, and more preferably 1000 mJ / cm ² or more, by irradiating the coating surface coated with the coating liquid composition of the present invention with a low-temperature transparent energy. A film with excellent properties such as resistance, environmental resistance, and scratch resistance, and which hardly causes cracks.

Drying and / or baking by heat may be simultaneously performed while irradiating ultraviolet rays. By simultaneously using a drying method by ultraviolet irradiation and a drying step by thermal drying at a temperature of preferably 250 ° C. or less, a coating film excellent in performance such as transparency, environmental resistance, and scratch resistance is given and laminated. Even in this case, it is possible to suppress film peeling and crack generation, which are likely to occur due to a difference in thermal shrinkage in the process of densification of the high refractive index film layer and the low refractive index film layer. By utilizing the ultraviolet irradiation as described above, the speed of the drying process can be increased, and the productivity can be dramatically improved.

As the transparent glass substrate in the present invention,
A transparent glass article having a refractive index of 1.47 to 1.53, for example, an uncolored glass plate having a transparent soda lime silicate glass composition, colored in green, bronze, or the like, or blocking ultraviolet rays or heat rays. A glass plate having performance or a transparent glass substrate having another shape may be used,
A glass plate for PDP or other displays, a glass plate for automobiles and a glass plate for buildings having a thickness of 0.5 mm to 5.0 mm are preferably used, and the antireflection colored film is provided on one surface or both surfaces of the glass plate. Can be coated. When both surfaces of a plate-shaped anti-reflection colored film-coated glass article are used in contact with air or other gas at normal pressure or reduced pressure, both surfaces of the glass substrate are coated with an anti-reflection colored film. Thereby, the visible light reflectance can be minimized. When one surface of the plate-shaped anti-reflection colored film-coated glass article is bonded to, or adhered to, various panels via, for example, a plastic film, the anti-reflection colored film is applied only to the other surface of the glass article. It is often sufficient to be coated.

The glass article coated with the antireflection colored film of the present invention,
In particular, a colored film-coated glass plate used for a front glass of a display device such as a PDP, an automobile window, an architectural window, or the like is preferably represented by a Lab color system, and a is -15.0.
２20.0, b has a transmission color represented by chromaticity in the range of −15.0 to 3.0. More preferably, in the Lab color system, a is -5.0 to 10.0, and b is -5.0 to 3.0.
It has a transmitted color represented by a chromaticity in the range of 0.

The glass article coated with an antireflection colored film according to the present invention provides a glass article having excellent reflection reducing properties utilizing selective absorption. In addition, the present invention provides a glass article excellent in design by a colored absorbing film. In addition, the glass article coated with the antireflection colored film of the present invention is combined with an electromagnetic wave shielding film and the like to form a PDP.
It can be used as an optical filter that is used in close contact with the front surface of a. In that case, since a selective absorption membrane is used, P
Provided is an optical filter for adjusting the emission color of DP. For example, in a PDP, a phosphor that emits blue light has a property of slightly emitting a red component in addition to blue. Therefore, when a portion that should be displayed in blue is displayed in a purplish color, the phosphor of the phosphor emits red light. The components are absorbed by the colored film of the present invention, and PDP
Emission colors from the LEDs can be balanced. When a silver multilayer film is used as the electromagnetic wave shielding layer, the transmission color of the conventional optical filter is yellow-green, but by using the anti-reflection coloring film of the present invention, the transmission color of which is reddish purple, The transmission color of the entire filter can be adjusted to a neutral gray color or a blue gray color. The above-mentioned optical filter for a plasma display panel in which the electromagnetic wave shielding layer is provided on the surface opposite to the surface coated with the anti-reflection colored film has a value of -3.0 to 3.0 in a Lab color system. ,
It is preferable that b has a transmission color represented by a chromaticity of -3.0 to 3.0. In addition to using a silver multilayer film as the electromagnetic wave shielding layer, a method of applying a high conductivity metal, such as copper or copper nickel, to a transparent substrate by electroless plating a synthetic resin mesh fabric on a transparent substrate may be used. Resistance ITO film,
A method of directly laminating a silver thin film and a multilayer film composed of a silver thin film on a transparent substrate, a method of laminating a film obtained by laminating these layers on a transparent substrate, and the like can be used.

The PDP has a front glass plate and a rear glass plate as its parts. The reflection of the present invention using a high strain point glass plate, ie, a glass substrate having a strain point of 570 ° C. or more, as a transparent glass substrate. By using the glass article coated with the protective film as a front glass plate of PDP,
An optical filter for a PDP can be used as a front glass plate of the PDP, and a PDP having an antireflection film on its surface can be provided.

[0038]

Next, the present invention will be described in more detail with reference to specific examples. [Preparation of stock solution] To 1 mol of titanium isopropoxide stirred in a flask, 2 mol of acetylacetone was added dropwise using a dropping funnel. This solution was used as titanium oxide stock solution 1.
It contains 16.5% TiO ₂ solids. Ethyl silicate (Colcoat Co., Ltd. “Ethyl silicate 4
0 ") 50g, 0.1N hydrochloric acid 6g and ethyl cellosolve 4
4 g was added and the mixture was stirred at room temperature for 2 hours. This solution was used as silicon oxide stock solution 2. It contains 20% SiO ₂ solids.

[Preparation of Liquid Composition for Film Forming] A liquid composition for forming a high refractive index film was prepared in accordance with the composition ratio shown in Table 1 as a coating liquid for the first layer counted from the glass substrate. A predetermined amount of a titanium oxide stock solution 1, a solvent (ethyl cellosolve), a silicon oxide stock solution 2, and a gold raw material (chloroauric acid tetrahydrate) were mixed in this order and stirred at room temperature for 2 hours to obtain a coating solution number (H1 to H1).
A liquid composition for forming a high refractive index film shown in 5) was obtained. Similarly, the coating liquid numbers (L1 to L
A liquid composition for forming a low refractive index film shown in 15) was obtained.

[Examples 1 to 15 and Comparative Examples 1 to 4] The above-prepared coating solution H1 was used to prepare a 1.1 cm thick 10 cm
Spin coating was performed for 15 seconds at a rotation speed of 3000 rpm on one surface of a non-colored transparent glass substrate (refractive index = 1.50) of soda-lime silicate composition having a size of × 10 cm. After air drying, heat treatment was performed at 550 ° C. for 2 minutes to cover the high refractive index colored film.
Spin coating at 000 rpm for 15 seconds, heat-dry at 550 ° C. for 2 minutes after air drying to coat the low refractive index film, and form an antireflection colored film composed of a high refractive index colored film and a low refractive index film formed thereon. A coated glass plate was obtained. The visible light reflectance Rvis of this glass plate is such that the D light source light is incident at an angle of 12 degrees from the film surface coated with the colored film, and the reflected light from the back surface (non-film surface) is blocked. Only two types of reflectance were measured, namely, the reflectance (“Rvis film surface”) and the reflectance including the reflection from the back surface side and the film surface side (“Rvis both surfaces”). Visible light transmittance Tvis (D light source light) is JIS R
According to 3106, the chromaticity of transmitted light is determined according to JIS Z
8729.

The compositions, refractive indices, and film thicknesses of the high refractive index film and the low refractive index film are as shown in Tables 3 and 4, and include visible light transmittance (Tvis), chromaticity of transmitted light, and visible light reflectance. (Rvis) was as shown in Table 5. Further, the obtained colored film showed good results in chemical resistance and abrasion resistance. When the antireflection colored film is coated on both surfaces of the glass substrate, the reflectance including the reflection from the front side and the back side (“Rvis both sides”) is obtained by applying the antireflection colored film to only one surface of the glass substrate. Reflectance (“Rvi
s both sides "), which was smaller than 3.8% and 1.2%.

Similarly, the coating solutions (H2
To H15 and L2 to L15), coated with an antireflection colored film coated with a high-refractive-index film and a low-refractive-index film having compositions, refractive indices, and film thicknesses as shown in Tables 3 and 4, respectively. (Examples 2 to 15) were obtained. Table 5 summarizes the measurement results of these optical characteristics.

In Examples 1 to 8, as shown in Table 5, the red color is absorbed and the transmitted color is green, that is, a = -3.1 to -8.4 and b = -2 in the Lab color system. Transmitted light chromaticity of 0.9 to -7.8, reflectance only on the film surface side ("Rvis film surface")
Was 1.0% or less.
In Examples 9 to 11, the yellow color is absorbed and the transmission color is blue, that is, a = 0.3 to 0.8 and b = − in the Lab color system.
An antireflection film-coated glass article having a transmitted light chromaticity of 3.5 to -10.5 and a reflectance (“Rvis film surface”) only on the film surface side of 1.0% or less was obtained. In Examples 12 to 15, green is absorbed and the transmission color is purple to magenta, that is, a = 2.4 to 9.8 and b = −5.3 to −1.8 in the Lab color system. It is the chromaticity of transmitted light, and the visible light reflectance (“Rvi
The glass article coated with an antireflection film having an “s film surface” of 1.0% or less was obtained. All of the glass articles coated with the antireflection film of Examples 1 to 15 had a visible light transmittance (Tvi) of 60% or more.
s).

As shown in Tables 6 and 7, by adjusting the rotation speed by spin coating, which is the application condition of the coating liquid for forming a high refractive index film or the coating liquid for forming a low refractive index film, Except that the thickness of the film was changed out of the range of 80 to 140 nm, or the thickness of the low refractive index film was changed out of the range of 70 to 99 nm, the antireflection colored film-coated glass article ( Comparative Examples 1 to 4) were obtained. Table 8 shows the measurement results of the optical characteristics. In the comparative example,
The visible light reflectance (“Rvis film surface”) only on the film surface side is 3.0 to 3.0.
It was 4.2%, and the visible light antireflection performance was clearly inferior to the examples (0.4 to 0.9%). The visible light transmittance (Tvis) of the comparative example was less than 60%, which was inferior to the examples (60% or more).

[0045]

[Table 1] Example coating liquid Titanium oxide Silicon oxide Gold raw material Solvent number No. Stock solution 1 (g) Stock solution 2 (g) (g) (g) ───────────────────────────────── ─ 1 H1 25.8 0 1.3 73.0 2 H2 22.1 3.0 1.3 73.6 3 H3 20.6 4.3 1.3 1.3 73.9 4 H4 18.5 6.0 1 .3 74.2 5 H5 15.5 6.5 2.0 76.1 6 H6 17.3 7.0 1.3 74.4 7 H7 18.5 7.8 0.7 73.18 H8 14 .6 9.3 1.3 74.9 9 H9 7.9 12.8 2.0 77.4 10 H10 8.5 14.3 1.3 76.0 11 H11 9.4 15.3 0.7 74.7 12 H12 10.0 16.8 0 73.3 13 H13 10.0 16.8 0 73.3 14 H14 10.0 16.8 0 73.3 15 H15 9.7 16.1 0.35 73.9 16 H16 10.0 16.8 0 73.3 ──────────────────────────

[0046]

[Table 2] Example coating liquid Silicon oxide Au raw material Solvent No. No. Stock solution 2 (g) (g) １ 1 L1 25.0 0 75 0.02 L2 25.0 0 75.0 3 L3 25.0 0 75.0 4 L4 25.0 0 75.0 5 L5 25.0 0 75.0 6 L6 25.0 0 75.0 7 725 0.0 75.08 L8 25.0 0 75.0 9 L9 25.0 0 75.0 10 L10 25.0 0 75.0 11 L11 25.0 0 75.0 12 L12 19.3 2.0 78.8 13 L13 21.3 1.3 77.5 14 L14 23.0 0.7 76.3 15 L15 24.0 0.26 75.7 16 L16 24.0 0.3 75.7 ─── ────────────────────────────

[0047]

[Table 3] Example: High refractive index film composition (% by weight) Refractive index Thickness number TiO ₂ SiO ₂ Au (nm) ─────────────────────────────────── 185 0 15 2.20 100 2 73 12 15 2.07 101 3 68 17 15 2.00 107 4 61 23 15 15 .95 108 5 51 26 23 1.86 108 6 57 28 15 1.86 108 7 61 31 8 1.86 111 848 37 15 1.80 110 9 926 51 23 1.76 123 10 28 57 15 1.76 122 11 31 61 61 8.1.76 120 12 33 67 0 1.76 101 13 33 67 0 1. 76 101 14 33 67 0 1.76 100 15 326 4 1.76 105 16 33 67 0 1.76 100 ───────────────────────────────────

[0048]

[Table 4] Example Low refractive index film composition (% by weight) Refractive index Thickness number SiO ₂ Au (nm) ─────────────────────────────────── 1 100 0 1 .46 77 2 100 0 1.46 773 100 0 1.46 784 4 100 0 1.46 795 100 0 1.46 796 6 100 0 1.46 807 100 0 1.46 808 001. 46 80 9 100 0 1.46 81 10 100 0 1.46 81 11 100 0 1.46 81 12 77 23 1.46 87 13 85 15 1.46 90 14 92 8 1.46 91 15 973 1.46 92 16 96 4 1.46 91 ──────────────────────────── ───────

[0049]

[Table 5] ───────────────────────────────── Transmitted light Chromaticity of transmitted light Rvis (%) Tvis color tone ────────── ───────── number (%) a b film surface both sides ──────────────────── １ 171.0 Green -6.9 -3.4 0.6 0.6 3.8 2 72.2 Green -6.7 -3.3 0.7 3. 7 373.9 green -6.3 -2.9 0.6 0.6 3.8 74.0 green -6.2 -4.1 0.8 3.6 5 66.2 green -8.4-7 .8 0.4 3.0 674.1 green -5.6 -5.2 0.7 3.6 67 82.0 green -2.8 -2.6 0.9 0.9 4.08 73.4 Green -3.1 -6.5 0.6 3.7 9 64.8 Blue 0.8-10.5 0.4 3.4 10 73.2 Blue 0.5-7.0 0.7 3. 7 11 81.6 Blue 0.3 -3.5 0.9 4 .11 12 76.8 Red-purple 9.8-5.3 0.4 3.2 13 81.2 Red-purple 6.5 -3.5 0.7 3.7 148.5.6 Red-purple 3.3- 1.8 0.9 4.1 15 81.0 Purple 2.4-2.7 0.9 4.1 16 85.6 Red purple 2.5-0.8 0.9 4.3 ──── ─────────────────────────────

[0050]

[Table 6] Comparative example Coating liquid High refractive index film composition (weight %) Refractive index Thickness number No. TiO ₂ SiO ₂ Au (nm) ────────────────────────────────── {1 H5 512 2623 1.86 702 H5 51 2623 1.86 160 3 H5 5126 23 1.86 108 4 H5 51 2623 1.86 108} ──────────────────────

[0051]

[Table 7] 比較 Comparative example Coating liquid Low refractive index film composition (weight %) Refractive index Thickness number No. SiO ₂ Au (nm) １ 1 L5 100 0 1.46 77 2 L5 100 0 1.46 773 3 L5 100 0 1.46 504 L5 100 0 1.46 120 ─────────────────── ────────────────

[0052]

[Table 8] 色 Chromaticity of transmitted light Rvis (%) Comparative Example Tvis ───────── 番号 Number (%) a b Membrane surface Both surfaces ────────────────────── １ 158.0 -7.9 -7.4 3.0 6.3 25.5.2 -7.7 -7.3 4.0 7.13 56.9 -7.3 -7.9 3.2 6.6 4 54.0 -7.2 -7.1 4.2 7.6 ─────────────── ────────────────────

Example 16 Production of Optical Filter 59 cmx whose surface was polished and washed with a cerium oxide abrasive.
A coating solution H shown in Table 1 was applied to one surface of an uncolored float glass plate (strain point: 575 ° C., refractive index = 1.50) having a high strain point of 89 cm and a thickness of 3.2 mm by a flexographic coating method.
16 and irradiated with ultraviolet light for 30 seconds at an irradiation intensity of 15 mW / cm ² from a distance of 10 cm using a high-pressure mercury lamp of 160 W / cm, and the composition shown in Table 3 was obtained.
A first layer high refractive index film having a refractive index and a film thickness, respectively, was formed. Subsequently, the coating liquid L16 shown in Table 2 was applied onto the first layer film, and heated to a glass temperature of 250 ° C. in a conveyor-conveying infrared heating furnace (in-furnace temperature: 300 ° C.) to obtain a composition shown in Table 4. , A second layer of colored low refractive index film having a refractive index and a thickness. Thus, a glass plate coated with an antireflection colored film composed of a high refractive index colored film and a low refractive index film formed thereon was obtained. Table 5 shows the measurement results of the optical characteristics of the glass plate coated with the antireflection colored film.

A black ink as a light shielding layer is formed on the periphery (width of about 10 mm) of the glass surface (second surface) opposite to the surface (first surface) of the glass plate on which the antireflection coloring film is formed. Was printed by silk screen printing, and then a conductive silver paste was printed as a ground electrode on the black printed layer, and baked at 500 ° C. Then, on the entire second surface, the following multilayer film of silver and inorganic oxide fine particles was formed as an electromagnetic wave shielding layer by a sputtering method. This multilayer film is formed on the second surface of the glass plate by SnO ₂ (34) -ZAO (7) -AgPd
0.4 (8) -ZAO (7) -SnO 2 (50) -ZAO (7) -AgPd0.4
(9) -ZAO (7) -SnO 2 (52) -ZAO (7) -AgPd0.4
Fourteen layers were laminated in the order of (7) -ZAO (7) -SnO ₂ (35).
“ZAO” is a composite metal oxide film obtained by oxygen reactive sputtering from a metal target of Zn (94% by weight) and Al (6% by weight), and “AgPd0.4” is A
g (99.6 wt%) Pd (0.4 wt%) is an alloy film obtained by sputtering with an argon gas from a metal target. The value in parentheses is the film thickness (nm).
This multilayer film has a sheet resistance of 2.5Ω / □ and 12%
Near infrared transmittance. If this multilayer film is formed on one surface of an uncolored float glass plate, the transmission color tone (chromaticity) is represented by the Lab color system, and a = −2.
4, b = 0.7, indicating a yellow-green color. When a glass plate having an anti-reflection film on the first surface and an electromagnetic wave shielding layer formed on the second surface is closely attached to the PDP so that the electromagnetic wave shielding layer faces the PDP, a Newton ring which is an interference fringe is not generated. Then, as a debris scattering prevention film if the glass plate is broken, a plastic film having fine irregularities formed on the surface side facing the PDP is adhered to the second surface of the glass plate, and an optical filter for the PDP is formed. Obtained. The transmission color tone of the obtained optical filter is a = 0.2, b = 0.3
And showed a neutral gray.

Example 17 Instead of laminating a plastic film having fine irregularities on its surface in Example 16, a commercially available anti-reflection film (also a film of a material having a different refractive index having a different refractive index) is also used as a shatter-prevention film. A plurality of layers are deposited on the second surface of the glass plate, and the PDP
Optical filter was obtained.

[0056]

As described above in the detailed description of the invention,
ADVANTAGE OF THE INVENTION According to this invention, the antireflection performance of visible light is excellent, the color tone of transmitted light can be freely controlled, and the glass article coated with an antireflection colored film having high visible light transmittance can be obtained. Using this glass article coated with an anti-reflection colored film, a high-performance optical filter for PDP can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G09F 9/30 316 H01J 11/02 E H01J 11/02 G02B 1/10 A

Claims (11)

[Claims] 1. A transparent glass substrate having a refractive index of 1.47 to 1.53, a refractive index of 1.59 to 2.30 and a refractive index of 80 to
Has a thickness of 140 nm and is expressed as 0 to 85% by weight
Silicon oxide, 10-95% titanium oxide and 5
A high-refractive-index film containing 30% to 30% of fine gold particles is formed on the high-refractive-index film in a range of 1.35 to 1.58 and at least as compared with the refractive index of the high-refractive-index film. A refractive index of 0.20 less, and a film thickness of 70-99 nm;
An antireflection colored film-coated glass article comprising a low-refractive-index film containing 90 to 100% by weight of silicon oxide expressed in terms of% by weight. 2. A transparent glass substrate having a refractive index of 1.47 to 1.53, a refractive index of 1.59 to 2.30 and a refractive index of 80 to
Having a thickness of 140 nm, expressed in% by weight, 0-89%
A high refractive index film containing 11-100% titanium oxide, and forming 1.35 on the high refractive index film.
１．５1.58 and a refractive index of at least 0.20 smaller than the refractive index of the high refractive index film;
An anti-reflective colored film-coated glass article having a thickness of 10 nm and forming a low refractive index film containing 70 to 95% by weight of silicon oxide and 4 to 30% of fine gold particles by weight. 3. A transparent glass substrate having a refractive index of 1.47 to 1.53 and a refractive index of 1.59 to 2.30 and a refractive index of 80 to
Having a thickness of 140 nm, expressed in% by weight, 0-89%
Forming a high refractive index film containing silicon oxide, 10 to 100% titanium oxide and 0 to 30% gold fine particles,
On the high refractive index film, at least 0.20 in the range of 1.35 to 1.58 and the refractive index of the high refractive index film.
A low refractive index film having a small value of refractive index and a film thickness of 70 to 99 nm and containing 70 to 100% of silicon oxide and 0 to 30% of fine gold particles in weight% is formed. Here, an antireflection colored film-coated glass article wherein the sum of the content of the fine gold particles in the high refractive index film and the content of the fine gold particles in the low refractive index film is 4 to 30% by weight. 4. The glass article according to claim 1, wherein a is -15.0 to 20.0 and b is -15.0 to 1 in a Lab color system.
4. A transparent color having a chromaticity of 3.0.
The glass article coated with an antireflective colored film according to any one of the above. 5. The glass article is represented by a Lab color system, wherein a is -5.0 to 10.0 and b is -5.0 to 3.0.
The antireflection colored film-coated glass article according to any one of claims 1 to 3, which has a transmission color represented by the following chromaticity. 6. The glass article has a visible light reflectance of 6.0% or less (including light reflected from the back side at an incident angle of 12 degrees, from the coating surface side). The glass article coated with an antireflective colored film according to any one of the above. 7. The glass article has a visible light reflectance of the film surface of 1.0% or less (light is incident on the film surface side at an incident angle of 12 degrees and light reflected from the back surface is blocked). The glass article coated with an anti-reflection colored film according to claim 1. 8. A plasma display, characterized in that an electromagnetic wave shielding layer is provided on the surface of the glass article according to any one of claims 1 to 7 opposite to the surface coated with the antireflection colored film. Optical filter for panel. 9. The optical filter according to claim 1, wherein a is -3.0 to 3.0, and b is -3.0 to 3.0 in a Lab color system.
9. The optical filter for a plasma display panel according to claim 8, having a transmission color represented by the following chromaticity. 10. The colored antireflection film-coated glass article according to claim 1, wherein the transparent glass substrate is a transparent glass plate having a high strain point. 11. A plasma display panel using the glass article coated with a colored anti-reflection film according to claim 10 as a front glass.