JPH1154053A - Low reflection glass article and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low reflection glass article coated with optical multi- layer film which can reduce reflectance in a wide range of visible light area. SOLUTION: In this article, a first layer with an intermediate refractive index (n1) of 1.60-1.95 and a film thickness of (60-130 nm)/n1, a second layer with a high refractive index (n2) which is within a range of 1.91-2.60 and also not less than 0.20 bigger than the refractive index of the first layer mentioned above and a film thickness of (140-230 mn)/n2 and a third layer with a low refraction index (n3) which is within a range of 1.35-1.59) and not less than 0.20 smaller than the refractive index of the first layer and a film thickness of (110-150 nm)/n3 are laminated in this order on a transparent glass base substance with a refractive index of 1.47-1.53, and the second layer contains titanium oxide and other metal oxide for not less than 70 mol.%, in total, the third layer contains silicon oxide for 50-100 mol.% and other metal oxide for 0-10 mol.% in total and the first layer contains silicon oxide for 15-80 mol.% and other metal oxide for 20-70 mol.% in total.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a low-reflection glass article,
In particular, the present invention relates to a low-reflection glass article in which a surface of a transparent glass substrate is coated with an optical thin film to provide an antireflection function for visible light, a method of manufacturing the same, an optical filter using the low-reflection glass article, and a plasma display panel. Things.

[0002]

2. Description of the Related Art In order to reduce the surface reflectance of optical parts such as cameras and glasses, or display parts of OA electronic devices such as display panels, displays and display filters, etc. An antireflection system using a thin film is used. These anti-reflective coatings
In order to enhance visibility or further enhance the inherent optical characteristics, high transmittance as well as low reflectivity are required.

[0003] The reduction of the reflectance by the optical thin film is due to the light interference effect. For the three-layer optical multilayer film, for example, an intermediate refractive index (1.7) is formed on a transparent glass substrate (refractive index 1.52).
1) and a first layer having an optical thickness of a quarter wavelength;
A second layer having a high refractive index (2.43) and an optical thickness of one half wavelength, and a low refractive index (1.39) and one quarter
A low-reflection glass article in which three layers having an optical thickness of a wavelength are laminated in this order in three layers is known (for example, HKPulke).
r, "Coatings on Glass", P.402-403, Amsterdam, Elsevie
r, 1984), it is known that the wavelength region where the reflectance is close to zero can be increased, and at the same time, the reflection color can be improved.

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. It is known that an optical filter having a layer of a multilayer antireflection film for preventing reflection of external light and an electromagnetic wave shielding layer and correcting the emission color of the PDP is provided on the front surface of the PDP. For example, a colored transparent substrate (a plate made of an acrylic resin or a polycarbonate resin, in which a pigment that absorbs an excessive red component emitted from a PDP is dispersed in a resin plate, so that the color tone that should be originally blue appears purpleish An anti-reflection film (a film formed by stacking a plurality of films of materials having different refractive indices on a plastic film base material) is bonded to one surface of a substrate which is colored so as to prevent the occurrence of a transparent substrate with a transparent adhesive. On the other surface of the film, (1) a film (for example, P
A sputtered silver-inorganic oxide fine particle on the surface of an ET film, and (2) an anti-interference fringe film (for example, a 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, JP-A-9-306366)

[0005]

However, an optical thin film system that reduces the reflectance by utilizing the above-described light interference effect is described below.
Since each thin film is formed using a vacuum-based facility, the facility becomes large-scale.

On the other hand, the above-mentioned optical filter for PDP has a problem that a pigment is mixed in a resin plate and an antireflection film is stuck on the surface thereof, so that the production cost is increased.

The present invention has been made in order to solve such a problem, and a low-reflection glass article coated with an optical multilayer film capable of reducing the reflectance in a wide range of the visible light region is provided.
The purpose is to provide without requiring large-scale facilities.

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

[0009]

According to the present invention, there is provided a recording medium having a size of from 1.47 to 1.
1.6 on a transparent glass substrate having a refractive index of 1.53
Intermediate refractive index (n ₁ ) of 0 to 1.95 and (60 to 13
0 nm) / n ₁ , and
A second layer having a high refractive index (n ₂ ) within a range of 2.60 and at least 0.20 greater than the refractive index of the first layer, and a thickness of (140 to 230 nm) / n _2. A low refractive index (n ₃ ) and a value of (110 to 150 nm) / n ₃ within a range of 1.35 to 1.59 and at least 0.20 smaller than the refractive index of the first layer. A low-reflection glass article in which a third layer having a film thickness is laminated in three layers in this order, wherein the second layer is titanium oxide, cerium oxide, bismuth oxide, zirconium oxide, niobium oxide, And at least one metal oxide selected from the group consisting of tantalum oxides in a total amount of 70 mol% or more, and the third layer contains 50 to 100 silicon oxides.
Mol% and the metal oxide in a total amount of 0 to 10 mol%, and the first layer contains a silicon oxide in a content of 15 to 80 mol% and a total of the metal oxide in a content of 20 to 70 mol%. It is a low reflection glass article characterized by containing.

Hereinafter, the present invention will be described in detail. In the present invention, a first layer (intermediate refractive index film), a second layer (high refractive index film), and a third layer (low refractive index) are sequentially laminated on a transparent glass substrate having a refractive index of 1.47 to 1.53. refractive index (refractive index is defined by the value of light having a wavelength of 550nm unless otherwise noted. below same) respectively n _1, n ₂ of Ritsumaku)
If n ₃ , the range of the refractive index value (n ₁ ) of the first layer (intermediate refractive index film) is 1.60 to 1.95, and the refractive index value of the second layer (high refractive index film) The range of (n ₂ ) is 1.9
The refractive index of the third layer (low refractive index film) (n ₃ ) is in the range of 1 to 2.60 and at least 0.20 greater than the refractive index of the first layer. 1.35 to 1.59
And at least 0.20 smaller than the refractive index of the first layer. It is preferable that these refractive indices are selected so as to substantially satisfy the relationship of the following expression 1, that is, the value on the right side of the following expression 1 is 95 to 110% of the value on the left side. In other words, the first layer and the refractive index of the (intermediate refractive index layer) (n _1), the refractive index of the value of the second layer (high refractive index film) (n _2), and a third layer (low refractive index film refractive index value) (n ₃₎ preferably satisfies the following formula 2.

[0011]

[Equation 1] n ₂ × n ₃ = n ₁ ² (1)

[Number 2] _{0.95 × n 2 × n 3 ≦} n 1 2 ≦ 1.10 × n 2 × n 3 (2)

Further, in order to reduce the reflectance in the visible light region, the first layer has an optical film thickness of 60 to 120 nm, that is, a film of (60 to 120 nm) / n ₁ , and the second layer has a film thickness of 14 to 60 nm.
Optical thickness of 0 to 230 nm, ie, 140 to 230 n
m) / n ₂ and the third layer is 110-150 n
m optical film thickness, that is, (110-150 nm) / n ₃
Having a film thickness of

By doing so, it is possible to make the reflectance of light having a specific wavelength incident from the film surface side on the film surface side substantially zero.

The degree of the difference in the refractive index of each film due to the difference in the wavelength of light is defined by the refractive index dispersion coefficient ν as in the following equation (3).

[0015]

Ν = (n ₅₉₀ −1) / (n ₅₉₀ −n ₆₇₀ ) (3)

Here, n ₅₉₀ represents a refractive index at a wavelength of 590 nm, and n ₆₇₀ represents a refractive index at a wavelength of 670 nm.

The preferred ranges of the refractive index dispersion coefficient ν of the first layer (intermediate refractive index film), the second layer (high refractive index film), and the third layer (low refractive index film) are 13 to 30, 2 to 2, respectively. 12 and 50 or more. When the refractive index dispersion coefficient ν of each layer is out of the above range, it becomes difficult to obtain small visible light reflection. Table 1 summarizes the ranges of the refractive index, the optical film thickness, and the refractive index dispersion coefficient ν of the first to third layers. Thus the refractive index,
By selecting the optical film thickness and the dispersion coefficient, 0.5% or less,
More preferably, a low reflection glass article having a visible light reflectance (film surface) of 0.3% or less is obtained.

[0018]

Table 1 ================================ Refractive Index Thickness (nm) Refractive Index Dispersion Coefficient ν −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− First layer 1.60 to 1.95 (= n1) (60 ~130) / n ₁ 13~30 second layer 1.91~2.60 (= n2) (140~230) / n 2 2~12 third layer 1.35~1.59 (= n3) (110 150) / n ₃ 50 or more ==================================

The high refractive index film (second layer) in the present invention is
Group IB (Cu, Ag, Au), Group IIA (Be, Mg, Ca, Sr, Ba, Ra), Group IIB (Zn, Cd, Hg), Group IIIA (Sc, Y) , La,
Ac), Group IIIB (B, Al, Ga, In, Tl),
Group IVA (Ti, Zr, Hf, Th), Group IVB (C,
Si, Ge, Sn, Pb), Group VA (V, Nb, T)
a, Pa), group VB (N, P, As, Sb, Bi),
Group VIA (Cr, Mo, W, U), Group VIB (O, S,
Se, Te, Po), Group VIIA (Mn, Tc, Re,
Np), Group VIII (Fe, Co, Ni, Ru, Rh,
Among candidate oxides of the elements Pd, Os, Ir, Pt, Pu, Am, and Cm), titanium (Ti), cerium (C
e) an oxide of at least one metal selected from bismuth (Bi), zirconium (Zr), niobium (Nb), and tantalum (Ta) as a main component. These metal oxides are TiO ₂ , CeO ₂ , Bi ₂ O ₃ , Z
In terms of rO ₂ , Nb ₂ O ₅ , and Ta ₂ O ₅ , the total content is 70 mol%, preferably 80 mol%, more preferably 90 mol%. Other components that may be contained at less than 30 mol% include silicon oxides and coloring components described below.

The low refractive index film (third layer) according to the present invention contains 50 to 100 mol% of silicon oxide (silica), and contains titanium (Ti), cerium (Ce), and bismuth (B).
i) oxides of at least one metal selected from zirconium (Zr), niobium (Nb), and tantalum (Ta), respectively, with TiO ₂ , CeO ₂ , Bi ₂ O ₃ , Zr
O _2, Nb ₂ O _5, and in terms of Ta ₂ O _5, containing 0 to 10 mol% in their total. As this metal oxide, the same type as the metal oxide contained in the high refractive index film can be selected. By choosing this way,
Shrinkage coefficients of the low refractive index film layer and the high refractive index film layer in the curing process are close to each other, and cracks and film peeling are unlikely to occur. Further, the adhesion at the interface between the low refractive index film layer and the high refractive index film layer can be improved. When the high refractive index film contains a plurality of types of metal oxides, for example, two types of titanium oxide and bismuth oxide, the ratio of titanium oxide to bismuth oxide contained in the high refractive index film is It is preferable that titanium oxide and bismuth oxide are contained in the low refractive index film at substantially the same ratio. Other components that may be included include the coloring components described below.

Intermediate refractive index film (first layer) according to the present invention
Contains at least 15 to 80 mol% of a silicon oxide and is at least one selected from titanium (Ti), cerium (Ce), bismuth (Bi), zirconium (Zr), niobium (Nb), and tantalum (Ta). One type of metal oxide is TiO ₂ , CeO ₂ , Bi ₂ O ₃ , ZrO ₂ ,
Converted to Nb ₂ O ₅ and Ta ₂ O ₅ , a total of 2
0-70 mol% is contained. As this metal oxide, the same type as the metal oxide contained in the high refractive index film can be selected. With this choice, the contraction coefficients of the intermediate refractive index film layer and the high refractive index film layer in the curing process are close to each other, and cracks and film peeling are unlikely to occur. Further, the adhesion at the interface between the intermediate refractive index film layer and the high refractive index film layer can be improved. Intermediate refractive index film (first
As a preferred example of the layer), a liquid composition obtained by mixing respective liquid compositions for forming the high refractive index film (second layer) and the low refractive index film (third layer) of the present invention at an arbitrary ratio. An example is a film formed using an object.

In the present invention, at least one of the high refractive index film, the low refractive index film, and the intermediate refractive index film may contain a coloring component. Examples of such coloring components include ultrafine metal particles composed of one or more members selected from Group IB and Group VIII of the periodic table. Of these, gold (Au) and platinum (P
t), palladium (Pd), rhodium (Rh), silver (A
Noble metals such as g) can be exemplified, and gold is particularly preferred. These coloring component metal fine particles are 0.5
It is preferable that the content be contained in an amount of about 20 mol%.

As one specific form of each of the optical thin films of the high refractive index film (second layer), the intermediate refractive index film (first layer) and the low refractive index film (third layer) in the present invention, titanium oxide is used. Stuff,
Examples include films containing bismuth oxide and silicon oxide. Hereinafter, this film will be described.

When an optical thin film containing titanium oxide, bismuth oxide and silicon oxide is used as the high refractive index film, the content of silicon oxide is 30 mol% or less in terms of SiO ₂ . , Preferably 20 mol% or less, more preferably 10 mol% or less.

The ratio between titanium oxide and bismuth oxide in the high refractive index film containing titanium oxide, bismuth oxide and silicon oxide of the present invention is selected so as to maximize the refractive index of the film. Is preferred. The contents of titanium oxide and bismuth oxide in the thin film are determined by determining the oxidation state of titanium and bismuth by TiO ₂ and Bi ₂ , respectively.
Assuming O ₃ , TiO ₂ and Bi ₂ O _{3 can be} represented by a molar ratio.
The ratio of Bi ₂ O ₃ to the total, that Bi ₂ O ₃ / (T
iO ₂ + Bi ₂ O ₃ ) is preferably 1 to 96%, more preferably 2 to 60%, and still more preferably 3 to 50%.

As shown in FIG. 1, the contents of titanium oxide, bismuth oxide, and silicon oxide in the high refractive index film were as follows in the ternary composition of TiO ₂ —Bi ₂ O ₃ —SiO _2. represents TiO _2, Bi ₂ O _3, SiO ₂ molar ratio in the coordinate points _{(TiO 2, Bi 2 O 3} , SiO 2 each mole%), a (69,1,30), B (99,1, 0), C
(5,95,0) and D (3,67,30) must be within the range of a square ABCD,
Preferably, E (78, 2, 20), F (98, 2,
0), G (40, 60, 0), H (32, 48, 20)
And more preferably a ratio within the range of a square EFGH consisting of I (87,3,10) and J (97,3,3).
0), K (50, 50, 0), L (45, 45, 10)
Is a ratio within the range of the square IJKL. The content of titanium oxide, bismuth oxide, and silicon oxide in the high refractive index film is 2.06 in the range of the square ABCD.
A high refractive index film having the above refractive index is obtained. Similarly, a high refractive index film having a refractive index of 2.18 or more in the range of square EFGH and a refractive index of 2.30 or more in the range of square IJKL is obtained. can get. As described above, when an optical thin film containing titanium oxide, bismuth oxide, and silicon oxide is used as a high refractive index film, components other than the above components, such as cerium oxide, unless the refractive index is lowered so much, A small amount of zirconium oxide, tantalum oxide, neobium oxide, tungsten oxide, antimony oxide,
For example, it may be contained at 10% or less.

On the other hand, when an optical thin film containing titanium oxide, bismuth oxide and silicon oxide is used as the low refractive index film in the present invention, the content of silicon oxide is represented by mol% of SiO _2. , 70 mol% or more, a more preferable ratio is 80 mol% or more, and a further preferable ratio is 90 mol% or more.

As shown in FIG. 1, the contents of titanium oxide, bismuth oxide and silicon oxide in the low refractive index film are represented by Y (0, 0,
0, 100), Z (29.5, 0.5, 70), A '
(1.5, 28.5, 70), the ratio must be within the range of the triangle YZA ′, and Y (0, 0, 1)
00), B '(19.5, 0.5, 80), C' (8, 1
2,80), and the ratio is preferably in the range of a triangle YB'C ', and more preferably Y (0,
0, 100), D '(9.5, 0.5, 90), E'
(5, 5, 90) in the range of the triangle YD'E '.

An optical thin film containing titanium oxide, bismuth oxide and silicon oxide is converted into an intermediate refractive index film (first layer)
In the case of using a high refractive index film, the content of titanium oxide, bismuth oxide, and silicon oxide in the thin film is expressed in the same manner as in the case of the high refractive index film, as shown in FIG.
5, 0.5, 69), N (68, 1, 31), O (3.
5,65,5,31) and P (1.5,29.5,69). The ratio must be within the range of a square MNOP, and Q (39,1,60), R (58 .5,1.
5,40), S (24,36,40), T (16,2)
The ratio is preferably within the range of a quadrangular QRST consisting of U (43,2,4,60).
55), V (53, 2, 45), W (27.5, 27.
5, 45) and X (22.5, 22.5, 55) within the range of a square UVWX. When the content of the titanium oxide, bismuth oxide, and silicon oxide in the intermediate refractive index film is within the range of the square MNOP, the content is 1.70 to 2.0.
A high refractive index film having a refractive index of 5 is obtained. Similarly, a refractive index of 1.80 to 2.00 in the range of the square QRST and a refractive index of 1.85 to 1.95 in the range of the square UVWX are obtained. Is obtained.

When the optical thin film containing titanium oxide, bismuth oxide and silicon oxide of the present invention is used as a low refractive index film (third layer) or an intermediate refractive index film (first layer), It is preferable that the ratio between the titanium oxide and the bismuth oxide be close to the ratio between the titanium oxide and the bismuth oxide in the high refractive index film (second layer) to be laminated. By doing so, the difference in heat shrinkage between the intermediate refractive index film and the high refractive index film and the difference in heat shrinkage between the high refractive index film and the low refractive index film during firing are reduced, and cracks and film peeling are reduced. Can be prevented. Furthermore, the wavelength dispersion of the refractive index of the high refractive index film, the low refractive index film, and the intermediate refractive index film is close to each other, and the transmitted light color tone, the reflected light color tone, Optical characteristics such as light reflectance are improved.

As another specific embodiment of the low reflection glass article of the present invention, the high refractive index film (second layer) contains titanium oxide, and the intermediate refractive index film (first layer) contains titanium oxide and titanium oxide. The low refractive index film (third layer) contains silicon oxide, and the fine gold particles contain the high refractive index film (second layer).
Layer), an intermediate refractive index film (first layer) and a low refractive index film (third layer).
Layer) in at least one layer. This will be described below.

The intermediate refractive index film of the antireflection film of the present invention (first
Each component of the layer will be described below. Silicon oxide (Si oxide) is an essential component for adjusting the refractive index of the film, and the lower the content, the higher the refractive index of the film. Conversely, when the content is large, the refractive index decreases. The content of silicon oxide is 15 to 80 mol% in terms of SiO _2.
, Preferably from 30 to 78 mol%, more preferably from 35 to 74 mol%. Titanium oxide is necessary to increase the refractive index of the film, and the lower the content, the lower the refractive index of the film, and the higher the content, the higher the refractive index of the film. The content of titanium oxide is Ti
20 to 70 mol% in terms of O ₂ , preferably 2
It is 2 to 65 mol%, and more preferably 25 to 60 mol%. When the thickness of the intermediate refractive index film is too small, the antireflection effect is reduced. On the other hand, when the thickness is too large, the antireflection effect is reduced, and the film strength is reduced due to cracks. Yes, preferably 45-5
It is 5 nm, and more preferably 47 to 53 nm.
If the refractive index of the intermediate refractive index film is too low, a sufficient antireflection effect cannot be obtained, so that the refractive index is preferably from 1.60 to 1.9.
0, more preferably 1.65 to 1.85,
More preferably, it is 1.70 to 1.80.

The high refractive index film (second layer) in the present invention
The components are described below. Titanium oxide is necessary for forming a film and for increasing the refractive index of the film. When the content is low, the refractive index of the colored film is low. When the content is large, the refractive index of the film increases. The content of titanium oxide is 70 to ₁ in terms of TiO2.
00 mol%, preferably 80 to 100 mol%, more preferably 88 to 100 mol%. The content of silicon oxide is 0 to 30 mol% in terms of SiO _2.
And preferably 0 to 20 mol%, more preferably 0 to 12 mol%.

If the thickness of the high refractive index film is too small, the anti-reflection effect will be low. Conversely, if it is too thick, the anti-reflection effect will be low, and cracks will occur to reduce the film strength. ~ 105 nm, preferably 75 ~
It is 95 nm, more preferably 80 to 90 nm. If the refractive index of the film is too low, a sufficient antireflection effect cannot be obtained. Therefore, the refractive index is preferably from 1.91 to 2.30, more preferably from 1.96 to 2.30, and even more preferably 2. 01 to 2.30.

Each component of the low refractive index film (third layer) in the invention will be described below. Silicon oxide is necessary for film formation and for lowering the refractive index of the film, and the lower the content, the higher the refractive index of the film. When the content is large, the refractive index of the film becomes small. The content of silicon oxide is 85 to 100 mol% in terms of SiO _2, preferably from 90 to 100 mol%.

If the thickness of the low refractive index film is too small, the antireflection effect will be low. Conversely, if it is too thick, the antireflection effect will be low. ~ 105 nm, preferably 75 ~
It is 95 nm, more preferably 80 to 90 nm. If the refractive index of the film is too low, the antireflection effect cannot be sufficiently obtained, so that it is 1.35 to 1.59, preferably 1.35 to 1.50, and more preferably 1.3.
5 to 1.47.

Gold gives color to a high refractive index film, a medium refractive index film or a low refractive index film as coloring fine particles. If the content is too low, sufficient coloring will not be obtained, while if it is too high, the durability of the film will be reduced, or excess gold fine particles will come out of the film. Therefore, the content of the fine gold particles is 0.5.
-20 mol%, preferably 1-15 mol%, more preferably 1-11 mol%.

The high refractive index film, low refractive index film and intermediate refractive index film of the present invention can be formed by sputtering, CVD, or spray pyrolysis. Therefore, the sol-gel method is more preferable. For coating by the sol-gel method, spin coating, dip coating, flow coating,
Roll coating method, gravure coating method, flexographic printing method,
A screen printing method or the like is used.

An optical thin film containing, for example, titanium oxide, bismuth oxide, silicon oxide and fine gold particles is formed on the high refractive index film, low refractive index film and intermediate refractive index film in the present invention by a sol-gel method. In this case, the coating liquid composition is prepared by dissolving a hydrolyzable and condensable metal compound such as a titanium compound, a bismuth compound, a silicon compound, a cerium compound, a zirconium compound, a niobium compound, and a tantalum compound, and a raw material of fine gold particles in an organic solvent. It is obtained by doing.

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 triisopropoxaside (2,4-pentanedionate) and titanium diisopropoxide (bis-2,4-
Pentandionate), titanium allyl acetate triisopropoxide, titanium bis (triethanolamine) diisopropoxide, titanium di-n-butoxide (bis-2,4-pentanedionate) and the like are used.

As the bismuth compound, bismuth nitrate, bismuth acetate, bismuth oxyacetate, bismuth acetate, bismuth chloride, bismuth alkoxide, bismuth hexafluoropentadionate, bismuth t-pentoxide, bismuth tetramethylheptanedionate and the like are used. . As the cerium compound, cerium nitrate, cerium chloride and the like are used.

As the silicon compound, a compound obtained by mixing a silicon alkoxide with a solvent such as an 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.

The raw materials for the fine gold particles include 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.

As the cerium compound, cerium organic compounds such as cerium alkoxide, cerium acetylacetonate and cerium carboxylate can be suitably used. In addition, cerium inorganic compounds such as nitrates, chlorides and sulfates can be used, but cerium nitrates and cerium acetylacetonate are preferred from the viewpoint of stability and availability.

Examples of the zirconium compound include tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, tetra n-propoxy zirconium, tetraisopropoxy zirconium isopropanol complex, tetraisobutoxy zirconium, tetra n-butoxy zirconium, tetra sec-butoxy Zirconium, tetra-t-butoxyzirconium and the like can be conveniently used. Zirconium halide alkoxides such as zirconium monochloride trialkoxide and zirconium dichloride dialkoxide can also be used. A zirconium alkoxide obtained by chelating the above zirconium alkoxide with a β-ketoester compound is also preferably used. Examples of chelating agents include CH ₃ C, such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, and butyl acetoacetate.
OCH ₃ COOR, where R is CH ₃ , C ₂ H ₅ , C
₃ H ₇ , or C ₄ H ₉ ) acetoacetates can be listed, among which alkyl acetoacetates, especially methyl acetoacetate and ethyl acetoacetate, are relatively inexpensive. Is preferred. Although the degree of chelation of the zirconium alkoxide may be part or all, the molar ratio of (β-ketoester) /
Chelation at a ratio of (zirconium alkoxide) = 2 is preferable because the chelate compound is stable. A chelating agent other than the β-ketoester compound, for example, zirconium alkoxide chelated with acetylacetone, is insoluble in a solvent such as alcohol and precipitates, making it impossible to prepare a coating solution. Further, it is also possible to use an alkoxyzirconium organic acid salt in which at least one of the alkoxy groups of the above zirconium alkoxide is replaced by an organic acid such as acetic acid, propionic acid, butanoic acid, acrylic acid, methacrylic acid, stearic acid and the like.

As the niobium compound, niobium pentachloride, niobium pentaethoxide and the like are used. Examples thereof include niobium trimethoxy dichloride formed by dissolving niobium pentachloride in methyl alcohol, niobium triethoxy dichloride formed by dissolving in ethyl alcohol, and niobium triisopropoxy dichloride formed by dissolving in isopropyl alcohol. Further, niobium triethoxy acetylacetonate, niobium ethoxy diacetyl acetonate, or niobium triethoxy ethyl acetonate, niobium ethoxy diethyl acetonate generated by adding ethyl acetoacetate to niobium pentaethoxide, which is formed by adding acetylacetone to niobium pentaethoxide. Can be exemplified.

As the tantalum compound, tantalum methoxide, tantalum pentaethoxide, tantalum pentan-
Butoxide, tantalum tetraethoxide acetylacetonate and the like.

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. Further, a small amount of a stabilizer, a leveling agent, a thickener, and the like may be added as needed. The amount of the solvent used depends on the thickness of the high-refractive-index film, intermediate-refractive-index film and low-refractive-index film finally obtained, and also on the coating method to be employed.
Used to fall within the range of 20%.

After the above-mentioned coating liquid composition is applied by the above-mentioned coating method, it is dried and / or baked by heating at a temperature of 250 ° C. or more, and then, further, a step of applying the next coating liquid thereon and drying or And / or repeating the steps of heating and firing, the ultraviolet ray reflective glass article is completed.
The coating thus obtained has excellent properties such as transparency, environmental resistance, and scratch resistance. Even when the layers are stacked, the layers having a high refractive index, the layers having a medium refractive index, and the layers having a low refractive index can be obtained. It is possible to suppress film peeling and crack generation, which are likely to occur due to a difference in heat shrinkage in the process of densification of a film layer.

Instead of the above-described manufacturing method using drying and / or drying / firing by heating at 250 ° C. or higher, a light irradiation method described below can be used. That is, after applying the coating liquid composition by the application method,
This is a method in which a coating-drying step is repeated, in which a step of irradiating a coating film with an electromagnetic wave having a wavelength shorter than that of visible light is performed, and subsequently, a step of applying the next coating liquid is performed. 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 on 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. 36
Irradiate the coating film with an irradiation intensity of 10 mW / cm ² or more, preferably 50 mW / cm ² or more, more preferably 100 mW / cm ² or more, using a high-pressure mercury lamp that efficiently emits 254 nm and 303 nm with a main wavelength of 5 nm. It is desirable to do. Using such an ultraviolet light source, 1
MJ / cm ² or more, preferably 500 mJ / cm ² or more, more preferably to apply the 1000 mJ / cm ² or more radiation energy, the coating film surface coated with the coating composition of the present invention. Apply as many layers as necessary
After repeating the ultraviolet irradiation, if necessary, 500 to 80
Heat in oven heated to 0 ° C. for 10 seconds to 2 minutes. Thereby, a laminated film excellent in performance such as transparency, environmental resistance, and scratch resistance at a low temperature and hardly causing cracks is provided.

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 having excellent performance such as transparency, environmental resistance, and scratch resistance is given, and the lamination is performed. Even when the layers are stacked, it is possible to suppress film peeling and generation of cracks which are likely to occur due to a difference in heat shrinkage in the process of densification of the high refractive index film layer, the intermediate 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 glass substrate in the present invention, a transparent glass article having a refractive index of 1.47 to 1.53, for example, a non-colored transparent glass plate having a soda lime silicate glass composition, a green color, a bronze color, or the like can be used. Colored or UV,
Alternatively, a glass plate or the like having a performance of blocking heat rays may be used, and a glass plate for automobiles and a display glass plate having a thickness of 0.5 mm to 5.0 mm are preferably used, and one surface or both sides of the glass plate. The above laminated film can be applied to the surface.

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 a PDP or other display, a glass plate for an automobile, and a glass plate for a building having a thickness of 0.5 mm to 5.0 mm is preferably used, and one or both surfaces of the glass plate is coated with the antireflection film. can do. When used in a state where both surfaces of a plate-shaped anti-reflective coating coated glass article are in contact with air or other gas at normal or reduced pressure, an anti-reflective coating or an anti-reflective colored coating is formed on both surfaces of the glass substrate. , The visible light reflectance can be minimized. When one surface of a plate-like antireflection film-coated glass article is used, for example, by bonding or adhering to various panels via a plastic film, the antireflection film is coated only on the other surface of the glass article. It is often enough to just be there.

The low-reflection glass article colored with the antireflection film of the present invention, particularly the low-reflection glass plate coated with a coloring film used for a front glass of a display device such as a PDP, an automobile window, an architectural window, etc., is preferable. Expressed in Lab color system,
a has a chromaticity in the range of -15.0 to 20.0, b has a chromaticity in the range of -15.0 to 3.0, and L has a transmitted color represented by a lightness of 40 to 90. More preferably, in the Lab color system, a is-
5.0 to 10.0, b has a chromaticity in the range of -5.0 to 6.0, and L has a transmitted color represented by a lightness of 60 to 90.

The low-reflection glass article coated with the colored anti-reflection film of the present invention provides a glass article excellent in reflection reduction and a glass article excellent in design by a colored absorption film. In addition, the glass article coated with the anti-reflection colored film of the present invention is combined with an electromagnetic wave shielding film, etc.
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. Also, when a silver multilayer film is used as the electromagnetic wave shielding layer, the transmission color of the conventional filter becomes yellow-green, but by using the anti-reflection coloring film of the present invention, the transmission color of which becomes reddish purple,
The transmission color of the entire filter can be adjusted to a neutral gray color or a blue gray color. The 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 coloring film, L
In the ab color system, a is -3.0 to 3.0, and b is-
It preferably 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. A method of directly laminating a resistive ITO film, a silver thin film, and a multilayer film of a silver thin film on a transparent substrate, a method of laminating a film obtained by laminating these films 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, and the reflection of the present invention using a high strain point glass plate as a transparent glass substrate, that is, a glass substrate having a strain point of 570 ° C. or more. 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.

[0057]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to examples. Preparation of high refractive index film forming solution composition (H1 liquid): 24.
9 g of bismuth nitrate pentahydrate (bismuth raw material)
Mix with 8.6 g of 2-ethoxyethanol and add 170.
7 g of tetraisopropoxytitanium (titanium raw material) was added, and the mixture was stirred at 60 ° C. for 3 hours. After cooling to room temperature, a solution composition for forming a high refractive index film was obtained (H1 solution). In the H1 liquid, titanium and bismuth were TiO ₂ and Bi ₂ O ₃ respectively.
In terms of conversion, 96 and 4 mol% were contained.

Preparation of low refractive index film forming solution composition (L1 solution): 150 g of ethyl silicate ("Ethyl silicate 40" manufactured by Colcoat) was mixed with 132 g of ethyl cellosolve, and 18 g of 0.1 mol / l hydrochloric acid was added. Add at room temperature 2
The mixture was stirred for an hour (Liquid L1).

Preparation of High Refractive Index Film Forming Solution Composition (H2 Liquid): High refractive index film forming solution composition was prepared by mixing H1 liquid with L1 liquid such that the amount of SiO 2 becomes 10 mol% in terms of oxide. Was obtained (H2 solution). In the H2 liquid, silicon, titanium,
And bismuth are SiO ₂ , TiO ₂ and Bi _{2 respectively.}
The content was 10, 88.2 and 1.8 mol% in terms of O ₃ .

Preparation of high refractive index film forming solution composition (H3 liquid): High refractive index film forming solution was prepared by mixing H1 liquid with L1 liquid so that the amount of SiO ₂ becomes 30 mol% in terms of oxide. A composition was obtained (H3 solution). In the H3 liquid, silicon, titanium, and bismuth contained SiO ₂ , TiO ₂ , and Bi ₂ O ₃ , respectively.
In terms of conversion, the content was 30, 68.6, and 1.4 mol% each.

Solution composition for forming an intermediate refractive index film (M1 solution)
Preparation of: H1 solution was mixed with L1 solution such that the amount of SiO ₂ was 50 mol% in terms of oxide to obtain a solution composition for forming an intermediate refractive index film (M1 solution). In the M1 liquid, silicon, titanium, and bismuth contained SiO ₂ , TiO ₂ , and B, respectively.
In terms of i ₂ O ₃ , the content was 50, 49, and 1 mol% each.

Solution composition for forming an intermediate refractive index film (M2 solution)
Preparation of: The H1 solution was mixed with the L1 solution such that the amount of SiO ₂ was 70 mol% in terms of oxide to obtain a solution composition for forming an intermediate refractive index film (M2 solution). In the M2 liquid, silicon, titanium, and bismuth contain SiO ₂ , TiO ₂ , and B, respectively.
70, 29.4, and 0.6 mol% in terms of i ₂ O ₃
Was included.

Preparation of low-refractive-index film forming solution composition (L2 solution): A low-refractive-index film forming solution was prepared by mixing H1 solution with L1 solution such that the amount of SiO ₂ becomes 90 mol% in terms of oxide. A composition was obtained (L2 solution). In the L2 liquid, silicon, titanium, and bismuth are SiO ₂ , TiO ₂ , and Bi ₂ O ₃ , respectively.
In terms of conversion, the content was 90, 9.8, and 0.2 mol% each.

Preparation of High Refractive Index Film Forming Solution Composition (H4 Solution): High refractive index film forming solution composition having a coloring component by dissolving 1% by weight of chloroauric acid in H1 solution by weight% I got (H4 liquid)

Preparation of low-refractive-index film forming solution composition (L3 liquid): Low-refractive-index film forming solution composition having a coloring component by dissolving 1% by weight of chloroauric acid expressed in weight% in L2 liquid. I got (L3 liquid)

Solution composition for forming an intermediate refractive index film (M3 solution)
Preparation: 1% chloroauric acid expressed in% by weight in M2 solution was dissolved to obtain a low refractive index film forming solution composition having a coloring component. (M3 liquid)

[Examples 1 to 23, Comparative Examples 1 to 6] Uncolored transparent soda lime glass plate (thickness: 1.1 mm, visible light transmittance: 91.2%, visible light reflectance (surface on the incident light side) Only, 12 degree incidence): 4.03%, visible light reflectance (both surfaces; 12 degree incidence): 8.05%, Lab respectively.
Expressed by the chromaticity of the color system, the transmitted light chromaticity a = −0.39, b
= 0.2, transmitted light saturation ((a ² + b ² ) ^1/2 ) = 0.44, reflected light chromaticity a of only the surface on the incident light side a = 0.08, b = −
0.31, the reflected light saturation ((a ² + b ² ) ^1/2 ) = 0.32.
Reflected light chromaticity (both surfaces) a = 0.02, b = -0.4
0, the reflected light saturation ((a ² + b ² ) ^1/2 ) = 0.40) was washed with an alkaline aqueous solution for 20 minutes and then in ultrapure water for 20 minutes while irradiating with ultrasonic waves, and the substrate was washed. Obtained.

The above-mentioned M1 solution was applied to one surface of the substrate by a gravure coating method, and was 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. A one-layer film was formed.
Subsequently, the H1 solution was applied on the first layer film, and ultraviolet irradiation was performed using the high-pressure mercury lamp at the same distance, irradiation intensity, and irradiation time as above to obtain a second layer. Subsequently, the L2 solution was applied on the second layer, and ultraviolet irradiation was performed using the above high-pressure mercury lamp under the same conditions as above to form a third layer. This was heated in an electric furnace heated to 720 ° C. for 30 seconds to obtain a low reflection glass plate in which a first layer film, a second layer film, and a third layer film were laminated on the substrate surface in that order. The first layer,
The number of roll rotations in the gravure coating method of the second and third layers was changed to obtain various low reflection glass plates having different optical film thicknesses (Examples 1 to 6 and Comparative Examples 1 to 6).

Further, instead of the H1 liquid of the second layer liquid, H
Except using two liquids, it performed similarly to Examples 1-6 (Examples 7-12). Further, the same operation as in Example 1 was performed except that H3 solution was used instead of the H1 solution of the second layer solution (Example 13).

Instead of the first layer liquid M1 and the second layer liquid H1 in Examples 1 to 6, M2 liquid and H3 liquid were used, respectively.
Except using a liquid, it carried out similarly to Examples 1-6 (Examples 14-16). The same procedure as in Examples 14 to 16 was carried out except that the L1 liquid was used as the third layer liquid (Examples 17 to 2).
3).

Regarding the optical characteristics of the obtained low-reflection glass plate, the visible light reflectance Rvis and the visible light transmittance Tvis conform to “JIS Z 8722”, and the visible light reflectance is the reflectance at 12 ° incidence. It was measured. Here, the visible light reflectance of only the film surface (one surface) of the light incident from the film surface side is expressed as R (S) vis, and the light incident from the film surface side includes the reflection of the film surface and the reflection of the back surface. The visible light reflectance of both surfaces is denoted as R (D) vis. For each of the first to third layers, the refractive index (n) was measured by ellipsometry with respect to light having a wavelength of 550 nm by ellipsometry, and the film composition is shown in Table 2; Tables 3 and 4 show the defined refractive index dispersion coefficient (ν), film thickness (d), and optical film thickness (nd). The visible light reflectance R (S) vis only on the film surface,
Expressed in the chromaticity of the Lab color system, the reflected light chromaticities a and b of the light projected from the film surface side only on the film surface (one surface) and the reflected light chroma ((a ² + b ² ) ^{1 / 2} )) Table 5 to Table 6
In addition, the visible light reflectance R (D) vis of both surfaces including the back surface, the reflected light chromaticities a and b including the back surface reflection of light projected from the film surface side, and the reflected light chroma ((a ² +
b ² ) ^1/2 )) are shown in Tables 7 and 8, and the visible light transmittance Tvis, transmitted chromaticities a and b, and transmitted light saturation ((( Tables 9 and 10 show the respective values of a ² + b ² ) ^1/2 ). The visible light reflectance and reflected light chromaticity of only the film surface (one surface) are adjusted so that the back surface (non-film surface) of the glass plate is roughened, and a black paint is applied and cured to prevent light reflection on the back surface. Was measured.

FIG. 2 shows the spectral characteristics of light reflected on the film surface of the low reflection glass plate of Example 1 when light was incident from the film surface side. In the figure, 480 nm and 590
It can be seen that the reflectance of light having a wavelength of nm is 0.01% or less and the reflectance of light having a wavelength of 550 nm is 0.13%.

As shown in Examples 1 to 23, the visible light reflectance R (S) vis on the film surface of the low-reflection glass plate to which light was incident from the film surface side of the present invention was 0.12 to 0. .48% and 0.5% or less, which is much smaller than 4.03% of the visible light reflectance of the untreated glass substrate (only the surface on the incident light side). It can be seen that the effect of preventing light reflection is great. On the other hand, in Comparative Examples 1 to 6 in which the thicknesses of the respective films are out of the range, the visible light reflectance R (S) v on the film surface side is obtained.
Although is is 1.04 to 1.91%, which is smaller than the visible light reflectance (only the surface on the incident light side) of the untreated glass substrate, it is considerably larger than the value of the embodiment. I have.

The visible light reflectivity R (D) vis of both surfaces including the back surface is also 4.09-4.
47%, which is smaller than 8.05% of the untreated glass substrate. Further, the chroma of the reflected light on both surfaces including the back surface of Examples 1 to 23 was in the range of 0.26 to 3.82, not more than 5.0, and was changed from the value of the untreated plate of 0.40. Is very small and has a reflection color close to neutral gray. Further, the visible light transmittance Tvis of Examples 1 to 23 was 92.3 to 9
The visible light transmittance Tvis 9 of the untreated plate was 3.8%.
The value is higher than 1.2%.

Example 24 The M1 solution of Example 1 and H1
The liquid and L2 solutions were replaced with the M3, H4 and L3 solutions, respectively, in the same manner. The low-reflection glass obtained has a light gray color tone of transmitted light and an R (S) vis value of 0.11.
% And Tvis value were 90.2%.

[Table 2] =============================== Film Composition of Each Layer (mol%) Example / Comparative Example Layer Use Liquid SiO ₂ TiO ₂ Bi ₂ O ₃ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Examples 1 to 6 First layer M1 liquid 50 49 1 Comparative Examples 1 to 6 Second layer H1 liquid 0 96 4 Third layer L2 liquid 90 9.8 0.2 -------------------------------------- −−−−−−−−− First layer M1 liquid 50 49 1 Examples 7 to 12 Second layer H2 liquid 10 88.2 1.8 Third layer L2 liquid 90 9.8 0.2 −−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 1st layer M1 liquid 50 49 1 Example 13 2nd layer H3 liquid 30 68.6 1.4 3rd layer L2 liquid 90 9.8 0.2 ---------------------------------------------------------- 1st layer M2 liquid 70 29.4 0.6 Examples 14 to 16 Second layer H3 solution 30 68.6 1.4 Third layer L2 solution 90 9.8 0.2 --------------------------- −−−−−−−−−−−−−−−−− First layer M2 liquid 70 29.4 0.6 Examples 17 to 23 Second layer H3 liquid 30 68.6 1.4 Third layer L1 liquid 100 0 0 ==============================

[0076]

[Table 3] =================================== real first layer a second layer third layer facilities n ν film thickness nd n ν film thickness nd n ν film thickness nd Example d (nm) (nm) d (nm) (nm) d (nm) (nm) −−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−− 1 1 1.89 14.15 51 96 2.37 5.19 84 199 1.49> 100 83 124 2 1.89 14.15 41 77 2.37 5.19 84 199 1.49> 100 83 124 3 1.89 14.15 61 115 2.37 5.19 84 199 1.49> 100 83 124 4 1.89 14.15 51 96 2.37 5.19 74 175 1.49> 100 83 124 5 1.89 14.15 51 96 2.37 5.19 94 223 1.49> 100 83 124 6 1.89 14.15 51 96 2.37 5.19 84 199 1.49> 100 93 139 7 1.89 14.15 52 98 2.33 5.82 82 190 1.49> 100 84 125 8 1.89 14.15 42 79 2.33 5.82 84 196 1.49> 100 83 124 9 1.89 14.15 62 117 2.33 5.82 84 196 1.49> 100 83 124 10 1.89 14.15 52 98 2.33 5.82 72 167 1.49> 100 84 125 11 1.89 14.15 52 98 2.33 5.82 92 214 1.49> 100 83 124 12 1.89 14.15 52 98 2.33 5.82 82 190 1.49> 100 94 140 13 1.89 14.15 51 96 2.06 9.36 84 173 1.49> 100 83 124 14 1.71> 100 71 122 2.06 9.36 67 139 1.49> 100 88 131 15 1.71> 100 61 104 2.06 9.36 94 193 1.49> 100 80 119 16 1.71> 100 57 98 2.06 9.36 62 127 1.49> 100 83 123 17 1.71> 100 60 102 2.06 9.36 94 193 1.46> 100 83 121 18 1.71> 100 49 83 2.06 9.36 94 193 1.46> 100 83 121 19 1.71> 100 40 68 2.06 9.36 94 193 1.46 > 100 83 121 20 1.71> 100 70 119 2.06 9.36 94 193 1.46> 100 83 121 21 1.71> 100 80 136 2.06 9.36 94 193 1.46> 100 83 121 22 1.71> 100 60 102 2.06 9.36 74 152 1.46> 100 83 121 23 1.71> 100 49 84 2.06 9.36 87 179 1.46> 100 86 125 ===================================

[0077]

[Table 4] ================================== First Layer Second Layer Third Layer n ₁ ν Thickness n ₁・ dn ₂ ν Thickness n ₂・ dn ₃ ν Thickness n ₃・ dd (nm) (nm) d (nm) (nm) d (nm) (nm) −−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Comparative Example 1 1.89 14.15 31 58 2.37 5.19 199 84 1.49> 100 83 124 2 1.89 14.15 80 152 2.37 5.19 199 84 1.49> 100 83 124 3 1.89 14.15 51 96 2.37 5.19 128 54 1.49> 100 83 124 4 1.89 14.15 51 96 2.37 5.19 246 104 1.49> 100 83 124 5 1.89 14.15 51 96 2.37 5.19 199 84 1.49> 100 64 95 6 1.89 14.15 51 96 2.37 5.19 246 104 1.49> 100 103 154 ====================================

[0078]

[Table 5] ========================== Real Visible Light Reflected Light Chromaticity (Film Surface) Application Reflectivity (Film Surface) −−−−−−−−−−−−− Example R (S) vis (%) a b (a ² + b ² ) ^1/2 −−−−−−−−−−−−−−−−−− −−−−−−−−−−− 1 0.14 1.48 -0.92 1.74 2 0.43 -0.72 1.45 1.62 3 0.24 6.49 8.82 10.95 4 0.29 9.06 -0.81 9.10 5 0.48 -3.56 1.08 3.72 6 0.48 3.22 -8.12 8.74 7 0.13 1.57 -0.79 1.76 8 0.38 0.40 -0.66 0.77 9 0.26 5.22 -6.81 8.58 10 0.23 8.39 -0.92 8.44 11 0.40 -2.80 1.36 3.11 12 0.48 2.17 -7.72 8.02 13 0.14 1.48 -0.92 1.74 14 0.27 11.86 -10.09 15.57 15 0.35 3.91 -3.98 4.29 16 0.38 8.75 -10.30 13.51 17 0.19 5.74 -6.38 8.58 18 0.24 3.86 -8.48 9.32 19 0.38 3.82 -10.79 11.45 20 0.23 8.41 -5.78 10.20 21 0.37 10.38 -6.83 12.43 22 0.45 10.24 -1.50 10.35 23 0.12 3.82 -3.25 5.02 === =========== ===========

[0079]

Table 6 ========================== Visible Light Reflected Light Chromaticity (Film Surface) Reflectance (Film Surface) ------ −−−−−−−−−− R (S) vis (%) a b (a ² + b ² ) ^1/2 −−−−−−−−−−−−−−−−−−−−−−−− −−−−− Comparative Example 1 1.04 0.47 -0.71 0.85 2 1.44 8.36 -12.10 14.71 3 1.76 9.52 2.56 9.86 4 1.19 -2.99 2.42 3.85 5 1.91 1.71 -0.85 1.91 6 1.59 3.91 -10.40 11.11 ========= =================

[0080]

================================================================================================================================================================================================================================== −−−−−−−−−−−−− Example R (D) vis (%) a b (a ² + b ² ) ^1/2 −−−−−−−−−−−−−−−−− −−−−−−−−−−−− 1 4.12 0.18 -0.57 0.60 2 4.39 -0.26 -0.005 0.26 3 4.21 1.37 -2.33 2.70 4 4.26 2.12 -0.59 2.20 5 4.43 -1.16 -0.07 1.16 6 4.42 0.90 -2.84 2.98 7 4.09 0.24 -0.62 0.66 8 4.33 0.10 -0.68 0.69 9 4.21 1.18 -2.02 2.34 10 4.19 1.80 -0.67 1.92 11 4.40 0.64 -2.80 2.87 12 4.12 0.18 -0.57 0.60 13 4.12 0.18 -0.57 0.60 14 4.21 2.71 -2.53 3.71 15 4.21- 1.31 -2.53 2.85 16 4.33 2.37 -3.00 3.82 17 4.21 1.06 -1.55 1.88 18 4.27 0.80 -2.18 2.32 19 4.41 0.99 -3.26 3.41 20 4.25 1.76 -1.55 2.35 21 4.37 2.74 -2.12 3.46 22 4.47 2.95 -0.72 3.04 23 4.19 0.54- 0.98 1.12 ============== ==============

[0081]

[Table 8] =========================== Visible light Reflected light chromaticity (both sides) Reflectivity (both sides) ------ −−−−−−−−−−−−− R (D) vis (%) a b (a ² + b ² ) ^1/2 −−−−−−−−−−−−−−−−−−− −−−−−−−−−−− Comparative Example 1 4.96 0.15 -0.70 0.72 2 5.30 3.98 -6.14 7.32 3 5.63 4.9 1.02 5.01 4 5.09 -1.41 0.72 1.58 5 5.78 0.86 -0.81 1.18 6 5.44 1.89 -5.51 5.83 === ========================

[0082]

=============================================================================================================================================================== −−−−− Example Tvis (%) a b (a ² + b ² ) ^1/2 −−−−−−−−−−−−−−−−−−−−−−−−−− 1 93.0 -0.49 -0.09 0.50 2 92.8 -0.32 -0.32 0.45 3 92.9 -0.77 0.41 0.87 4 92.9 -0.80 -0.04 0.80 5 92.7 -0.29 -0.17 0.34 6 92.5 -0.69 0.49 0.85 7 92.8 -0.35 -0.29 0.45 8 92.6 -0.25- 0.37 0.45 9 92.6 -0.59 0.13 0.60 10 92.7 -0.61 -0.23 0.65 11 92.3 -0.48 0.25 0.54 12 93.0 -0.49 -0.09 0.50 13 93.0 -0.49 -0.09 0.50 14 92.5 -0.92 0.95 1.32 15 92.5 -0.92 0.95 1.32 16 92.5- 0.77 1.01 1.27 17 93.5 -0.58 0.36 0.68 18 93.6 -0.49 0.43 0.65 19 93.5 -0.50 0.62 0.80 20 93.4 -0.75 0.43 0.86 21 93.1 -0.99 0.62 1.17 22 93.5 -0.99 0.31 1.04 23 93.8 -0.54 -0.13 0.56 === =================== ==

[0083]

[Table 10]

[Examples 25 to 40, Comparative Examples 7 to 12] Preparation of stock solution 1 m of titanium isopropoxide stirred in a flask
Then, 2 mol of acetylacetone was added dropwise to the ol with a dropping funnel. This solution was used as a titanium oxide stock solution. This is TiO ₂
Of 16.5 mol%. 50 g of ethyl silicate ("Ethyl silicate 40" manufactured by Colcoat)
6 g of 0.1N hydrochloric acid and 44 g of ethyl cellosolve were added, and the mixture was stirred at room temperature for 2 hours. This solution was used as a silicon oxide stock solution.
It contains 20 mol% of SiO ₂ .

Preparation of Liquid Composition for Film Forming A liquid composition for forming an intermediate refractive index film was prepared as a coating liquid for the first layer, counting from the glass substrate, according to the composition ratio shown in Table 11 as follows. A predetermined amount of a titanium oxide stock solution, a solvent (ethyl cellosolve), a silicon oxide stock solution, and a gold (Au) raw material (chloroauric acid tetrahydrate) are mixed in this order, and the mixture is stirred at room temperature for 2 hours to prepare an intermediate refractive index film (first). Layer) Forming liquid composition coating liquids (M5 to M20) were obtained. Similarly, according to the composition ratios shown in Table 12, high refractive index film (second layer) forming liquid composition coating liquids (H5 to H20) were obtained. Similarly, a liquid composition coating liquid (L5 to L20) for forming a low refractive index film (third layer) was obtained according to the composition ratio shown in Table 13.

The coating solution M5 prepared above was applied to a thickness of 1.1 m.
Spin coating was performed on one side surface of a non-colored transparent glass substrate (refractive index = 1.52) of soda lime silicate composition having a size of 10 cm × 10 cm at a rotation speed of 3000 rpm for 15 seconds. After air-drying, heat-treat at 550 ° C. for 2 minutes to cover the intermediate refractive index film, and then spin-coat the coating solution H5 prepared above at 2,000 rpm for 15 seconds, and air-dry at 550 ° C. for 2 minutes. Heat treatment coated the high refractive index colored film. Further, the coating liquid L prepared above
5 was spin-coated at 2,000 rpm for 15 seconds, air-dried, and then heat-treated at 550 ° C. for 2 minutes.
In the first layer having a composition, a refractive index, a film thickness and an optical film thickness shown in Table 1, the medium refractive index film, the composition shown in Table 15, the refractive index,
A glass plate coated with a second layer high refractive index film having a film thickness and an optical film thickness and a colored low refractive index film having a composition, a refractive index, a film thickness and an optical film thickness shown in Table 16 was obtained. (Example 25). The visible light reflectance Rvis of this glass plate is the film surface side where 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 (“Rvis film surface”) and the reflectance including the reflection from the back surface side and the film surface side (“Rvis film surface”).
vis both sides "). Visible light transmittance Tvi
s (D light source light) was measured according to JIS R 3106, and chromaticity of transmitted light was measured according to JIS Z 8729. The measurement results include visible light transmittance (Tvis), chromaticity JS of transmitted light, and visible light reflectance (Rvis film surface and Rvis).
vis both sides) as shown in Table 17. 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 ") It was smaller than 3.0% and 1.2%.

Similarly, coating solutions (M6 to M20, H6 to H20, and L6 to L20) shown in Tables 11 to 13
Using, as shown in Table 14 to Table 16, the composition, refractive index,
And a glass article coated with an antireflection colored film (Examples 26 to 40) having a medium refractive index film, a high refractive index film, and a low refractive index film, respectively, having different thicknesses. Table 17 summarizes the measurement results of these optical characteristics.

Examples 25 to 30 and Examples 34 to 36
As shown in the figure, a = -8.4 to -1.1 and b =
An antireflection film-coated glass article having a transmitted light chromaticity of -7.8 to -1.2 and a reflectance on the film surface side only ("Rvis film surface") of 0.5% or less was obtained. Further, as shown in Examples 31 to 33, the transmission color is blue-violet, absorbing yellow, that is, La
In the b color system, a = 0.3 to 0.8 and b = -10.5 to
An antireflection film-coated glass article having a transmitted light chromaticity of −3.5 and a reflectance (“Rvis film surface”) only on the film surface side of 0.5% or less was obtained. Further, as shown in Examples 37 to 40, the green color is absorbed and the transmission color is reddish purple, that is, Lab.
In a color system, a = 2.5 to 9.8 and b = −5.3 to −0.2.
8 is the transmitted light chromaticity and the visible light reflectance only on the film surface side
An antireflection film-coated glass article having a (Rvis film surface) of 0.5% or less was obtained. All of the glass articles coated with the antireflection film of Examples 25 to 40 exhibited a visible light transmittance (Tvis) of 60% or more.

Using the coating solutions shown in Table 18, the spin-coating conditions, which are the application conditions of the coating solution for forming a high refractive index film, the coating solution for forming a medium refractive index film, or the coating solution for forming a low refractive index film, are used. As shown in Table 19, the antireflection colored film coating was performed in the same manner as in Example 29 except that the film thickness of the high refractive index film, the intermediate refractive index film, or the low refractive index film was changed by adjusting the rotation speed. Glass articles (Comparative Examples 7 to 12) were obtained. The measurement results of the optical characteristics are as shown in Table 20. In the comparative example, the visible light reflectance (“Rvis film surface”) only on the film surface side is 3.0 to 4.2%, which is smaller than the Rvis film surface (0.1 to 0.3%) of the embodiment. Thus, the visible light antireflection performance was clearly inferior.

[0090]

[Table 11] ================================== First Layer Coating Liquid Composition Example Coating Liquid Oxidation Titanium silicon oxide Au raw material Solvent No. No. Stock solution (g) Stock solution (g) (g) (g) −−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−− 25 M5 15.5 6.5 2.0 76.1 26 M6 17.3 7.0 1.3 73.1 27 M7 18.5 7.8 0.7 73.1 28 M8 13.0 8.3 2.1 76.7 29 M9 14.6 9.3 1.3 74.9 30 M10 15.8 10.0 0.7 73.6 31 M11 7.9 12.8 2 0.0 77.4 32 M12 8.5 14.3 1.3 76.0 33 M13 9.4 15.3 0.7 74.7 34-40 M14 to M20 10.0 16.807 .2 41 M21 11.0 18.4 0 70.6 ===================================

[0091]

[Table 12] =================================== Second Layer Coating Liquid Composition Example Coating Liquid Oxidation Titanium silicon oxide Au raw material Solvent No. No. Stock solution (g) Stock solution (g) (g) (g) ------------------------------------ −−−−−−− 25 to 33 H5 to H13 30.000 69.7 34 H14 23.3 0 2.0 74.7 35 H15 25.8 0 1.3 73.036 H16 27.9 0 0.7 71.4 37 to 40 H17 to H20 30.3 0 0 69.7 41 H21 42.4 0 0 57.6 ===================== ================

[0092]

[Table 13] ================================== Composition of Third Layer Coating Solution Example Coating Solution Oxidation Silicon Au raw material Solvent No. No. Stock solution (g) (g) (g) --------------------------------------------------- -25 to 36 L5 to L16 25.0 0 75.0 37 L17 19.3 2.0 77.5 38 L18 21.3 1.3 76.3 39 L19 23.0 0.7 76.3 40 L20 24 0.0 0.3 75.7 41 L21 28.8 0.4 70.8 =============================== ====

[0093]

Table 14 ================================== Example Intermediate Refractive Index Film Composition (mol%) Refractive index Thickness n ₁ · d number TiO ₂ SiO ₂ Au ₁ d (nm) (nm) −−−−−−−−−−−−−−−−−−−−−−−−−−−− 25 53.7 36.4 9.8 1.86 53 99 26 56.8 37.1 6.1 1.86 51 9527 57.8 39.1 3.1 1. 86 52 97 28 44.7 45.6 9.7 1.80 53 95 29 46.5 47.6 5.9 1.80 52 94 30 48.0 49.0 3.0 1.80 51 92 31 25 .2 65.7 9.0 1.76 53 933 32 25.5 69.0 5.5 1.76 52 92 33 26.9 70.3 2.8 1.76 51 90 34 27.0 73.0 0 1.76 50 88 35 27.0 73.0 0 1. 6 50 88 36 27.0 73.0 0 1.76 51 90 37 27.0 73.0 0 1.76 51 90 38 27.0 73.0 0 1.76 50 88 39 27.0 73.0 0 1.76 50 88 40 27.0 73.0 0 1.76 50 88 ===================================== ===

[0094]

Table 15 ================================== Example High refractive index film composition (mol%) refractive index film thickness n ₂ · d number _{TiO 2 SiO 2 Au n 2 d} (nm) (nm) --------------------------- 25 100 000 2.20 85 187 26 100 00 2.20 84 185 27 100 100 2.20 84 185 28 28 100 00 2.20 84 185 29 100 00 0 2. 20 85 187 30 100 100 0 2.20 84 185 31 100 100 0 2.20 84 185 32 100 00 2.20 85 187 33 100 00 2.20 84 185 34 89.2 0 10.8 2.20 86 189 35 93.3 0 6.7 2.20 85 187 36 96.6 0 3.4 2.20 84 185 37 100 00 00 0 84 185 38 100 0 0 2.20 84 185 39 100 0 0 2.20 84 185 40 100 0 0 2.20 84 185 =================== ===============

[0095]

Table 16 ================================== Example Low refractive index film composition (mol%) Refractive index Thickness n ₃ · d number SiO ₂ Aun ₃ d (nm) (nm) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− ------------ 25 100 0 1.46 81 118 26 26 100 0 1.46 79 115 27 100 0 1.46 78 114 28 100 0 1.46 79 115 29 100 0 1.46 79 115 30 100 0 1 .46 80 117 31 100 0 1.46 80 117 32 100 0 1.46 80 117 33 100 0 1.46 81 118 34 100 0 1.46 81 118 35 100 0 1.46 81 118 36 100 0 1.46 82 120 37 91.6 8.4 1.46 83 121 38 94.9 5.1 1.46 82 120 399 .4 2.6 1.46 83 121 40 98.7 1.3 1.46 82 120 ============================ =====

[0096]

Table 17 ================================== Example TVIS Chromaticity of Transmitted Light RVIS (% ) No. (%) a b Membrane surface Both surfaces --------------------------------------------- 8.4-7.8 0.2 3.0 26 74.1-5.6-5.2 0.2 3.6 27 82.0-2.8-2.6 0.3 4.0 28 73.4 -3.1 -6.5 0.2 3.2 29 82.3 -2.1 -4.3 0.2 3.5 30 91.1 -1.1 -2.1 0.3 3.7 31 64.8 0.8 -10.5 0.1 3.2 32 73.2 0.5 -7.0 0.2 3.5 33 81.6 0.3 -3.5 0. 3 4.1 34 71.0 -6.9 -3.4 0.1 0.1 3.3 35 81.0 -4 6 -2.3 0.2 3.5 36 91.0 -2.3 -1.2 0.3 3.7 3776.8 .8 9.8 -5.3 0.2 3.2 38 81.2 6.5 -3.5 0.2 3.8 39 85.6 3.3 -1.8 0.2 4.1 40 85.6 2.5 -0.8 0.3 4.1 === ===============================

[0097]

[Table 18] ============================ Comparative Example Layer Working Solution Film Composition of Each Layer (mol%) TiO ₂ SiO ₂ Au −−−−−−−−−−−−−−−−−−−−−−−−−−−−− First layer M9 liquid 26.9 70.3 2.8 7 to 12 Second layer H9 liquid 100 0 0 Third layer L9 liquid 0 100 0 ==================================

[0098]

[Table 19] ================================== ratio second layer the first layer third layer compare refraction Index Thickness n ₁・ d Refractive index Thickness n ₂・ d Refractive index Thickness n ₃・ d Example n ₁ d (nm) (nm) n ₂ d (nm) (nm) n ₃ d (nm) (nm ) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 7 1.76 30 53 2.20 85 187 1.46 80 117 8 1.76 75 132 2.20 84 185 1.46 81 118 9 1.76 50 88 2.20 60 132 1.46 80 117 10 1.76 50 88 2.20 110 242 1.46 82 120 11 1.76 50 88 2.20 80 176 1.46 60 88 12 1.76 50 88 2.20 81 178 1.46 120 175 ====== =============================

[0099]

Table 20 ================================= Chromaticity of Transmitted Light Rvis (%) Comparative Example Tvis-----------------Number (%) a b Membrane surface Both sides------------------------------------------------ −−−−−−−−−−−− 7 788.0 −0.9 −3.4 3.0 6.3 8 75.2 −0.7 −3.3 4.0 7.1.19 76.9 -0.3 -3.9 3.2 6.6 10 74.0 -0.2 -3.1 4.2 4.2 7.6 11 76.9 -0.3 -3.9 3.2 6.6 12 74.0 -0.2 -3.1 4.2 7.6 ============================= =======

Example 41 A non-colored float glass plate having a high strain point of 59 cm × 89 cm and a thickness of 3.2 mm (strain point of 57 cm × 89 cm), which was polished and washed with a cerium oxide abrasive.
5 ° C.) was coated with a coating solution M21 having a composition shown in Table 11 by a flexo coating method.
Using a high-pressure mercury lamp of W / cm, ultraviolet irradiation was performed at an irradiation intensity of 15 mW / cm2 for 30 seconds from a distance of 10 cm to form a first layer film. Subsequently, a coating solution H21 having a composition shown in Table 12 was applied on the first layer film,
Using a high-pressure mercury lamp of 0 W / cm, ultraviolet irradiation was performed at an irradiation intensity of 15 mW / cm 2 for 30 seconds from a distance of 10 cm to form a second layer film. Further, a coating solution L21 having the composition shown in Table 13 was applied on the second layer film, and heated to a glass temperature of 250 ° C. in a conveyor-conveying infrared heating furnace (furnace temperature: 300 ° C.) to form the first layer. An antireflection film comprising a medium refractive index film, a second layer high refractive index film and a third layer colored low refractive index film was formed on the surface of the glass plate.

The peripheral portion (width of about 1) of the surface (second surface) of the glass plate opposite to the surface (first surface) on which the antireflection film is formed.
0 mm), a black ink is printed as a light shielding layer by silk screen printing, and subsequently, a conductive silver paste is printed as a ground electrode on the black printing layer,
Fired at ℃. Then, a silver multilayer film was formed as an electromagnetic wave shielding layer over the entire surface (second surface) by a sputtering method. If this silver multilayer film is formed on one surface of an uncolored float glass plate on which an antireflection film is not formed, the transmission color tone (chromaticity) is expressed in Lab color system, and a =
At -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 placed in close contact with the electromagnetic wave shielding layer so as to face the PDP, Newton rings, which are interference fringes, are not generated. Then, as a debris scattering prevention film when the glass is broken, a plastic film (Anti-glare film) having fine irregularities formed on the surface is laminated on the electromagnetic wave shielding layer on the second surface of the glass plate, An optical filter for PDP was obtained. The transmission color tone of the obtained optical filter was a = 0.2 and b = 0.3, indicating neutral gray.

Example 42 Instead of laminating a plastic film having fine irregularities on its surface in Example 41, a commercially available antireflection film (also a film of a material having a different refractive index) also serving as a shatter scattering prevention film was used. Are laminated and vapor-deposited.) On the second surface of the glass plate, and PD
An optical filter for P was obtained. Its optical characteristics were almost the same as those of Example 41.

[0103]

As described above in the detailed description of the invention,
According to the present invention, a low-reflection glass article having a visible light reflectance of 0.5% or less on a film surface can be obtained. Further, according to the present invention, a glass article coated with an antireflection colored film having an excellent antireflection performance for visible light, capable of freely controlling the color tone of transmitted light, and having high visible light transmittance, and a P article using the same.
An optical filter for DP is obtained.

[Brief description of the drawings]

FIG. 1 is a graph showing an example of a preferred composition of a high refractive index film layer, an intermediate refractive index film layer, and a low refractive index film layer in the present invention.

FIG. 2 is a graph showing reflectance spectral characteristics of one example of the low reflection glass article of the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02B 1/11 G02B 5/28 5/28 G09F 9/30 312 G09F 9/30 312 G02B 1/10 A

Claims (17)

[Claims] 1. An intermediate refractive index (n ₁ ) of 1.60 to 1.95 and a film thickness of (60 to 130 nm) / n ₁ on a transparent glass substrate having a refractive index of 1.47 to 1.53. A high refractive index (n ₂ ) in the range of 1.91 to 2.60 and at least 0.20 greater than the refractive index of said first layer, and (140 to 230 nm) / N ₂
A second layer having a thickness of 1.35 to 1.59 and at least 0.2 relative to the refractive index of the first layer.
0 low values of the low refractive index (n ₃ ) and (110-150
a third layer having a thickness of (nm) / n ₃ in this order, wherein the second layer is composed of titanium oxide, cerium oxide, bismuth oxide, and zirconium oxide. , Niobium oxide, and at least one metal oxide selected from the group consisting of tantalum oxide in a total amount of 70 mol% or more, and the third layer contains 50 to 100 mol% of a silicon oxide. And the first layer contains silicon oxide in an amount of 15 to 80 mol% and the metal oxide in a total amount of 20 to 70 mol%. A low reflection glass article characterized by the following. 2. The first layer has a refractive index dispersion coefficient of 13 to 30, the second layer has a refractive index dispersion coefficient of 2 to 12, and the third layer has a refractive index dispersion of 50 or more. The low-reflection glass article according to claim 1 having a coefficient. 3. The low reflection according to claim ₁ , wherein the first, second, and third layers have refractive indices n ₁ , n ₂ , and n ₃ that satisfy the following equation (2). Glass articles. [Number 2] _{0.95 × n 2 × n 3 ≦} n 1 2 ≦ 1.10 × n 2 × n 3 (2) 4. The metal oxide included in the third layer is the same as the metal oxide included in the second layer, and the metal oxide included in the first layer is the same as the metal oxide included in the first layer. 2. The same as the metal oxide contained in the two layers.
4. The low-reflection glass article according to any one of items 3 to 3. 5. At least one of the first to third layers
The layer according to any one of claims 1 to 4, wherein the layer contains 0.5 to 20 mol% of fine particles of at least one metal selected from the group consisting of groups IB and VIII of the periodic table.
Item 6. The low reflection glass article according to item 1. 6. The first layer contains 15 to 80 mol% of silicon oxide, and 20 to 70 mol% of titanium oxide, the second layer has 0 to 30 mol% of silicon oxide, and 70 to 100 mol% of titanium oxide, the third layer contains 85 to 100 mol% of silicon oxide, and at least one of the first, second and third layers has a thickness of 0 to 100%. 6. The composition according to claim 1, which contains from 0.5 to 20 mol% of fine gold particles.
The low reflection glass article according to any one of the above. 7. The method according to claim 1, wherein the first layer comprises a titanium oxide, a bismuth oxide, and a silicon oxide formed of TiO ₂ —Bi ₂ O ₃ —
TiO ₂ , Bi in SiO ₂ ternary composition
The molar ratio of ₂ O ₃ and SiO ₂ is calculated by using coordinate points (TiO ₂ , Bi
M (30.5, expressed by mol% of ₂ O ₃ and SiO ₂ )
0.5, 69), N (68, 1, 31), O (3.5, 6)
5.5, 31), and P (1.5, 29.5, 69) in a ratio within the range of a square MNOP, wherein the second layer comprises titanium oxide, bismuth oxide, and silicon oxide. An object is also represented by the coordinate point, and A (69,
1,30), B (99,1,0), C (5,95,
0) and a square AB consisting of D (3,67,30)
The third layer contains a titanium oxide, a bismuth oxide, and a silicon oxide in the same manner as the coordinate point represented by Y (0,0,100), Z ( 2
9.5, 0.5, 70) and A '(1.5, 28.
The low-reflection glass article according to any one of claims 1 to 4, wherein the low-reflection glass article is contained in a ratio within the range of the triangle YZA '. 8. The transparent glass substrate has a thickness of 0.5 to 5.0 m.
The low reflection glass article according to any one of claims 1 to 7, which is a glass plate having a thickness of m. 9. The glass article according to the present invention, wherein a is -15.0 to 20.0 and b is -15.0 to 0 in a Lab color system.
9. The low reflection glass article according to claim 8, having a transmission color represented by a chromaticity of 3.0. 10. The glass article is represented by a Lab color system, wherein a is -10.0 to 10.0, and b is -12.0 to
The low reflection glass article according to claim 9, having a transmission color represented by a chromaticity of 0.0. 11. The glass article has a visible light reflectance of 5.0% or less (visible light reflection on both surfaces including reflection on the film surface and reflection on the back surface for light incident from the film surface side at an incident angle of 12 degrees). The low-reflection glass article according to any one of claims 1 to 10, which has a (ratio). 12. The low reflection glass article according to claim 1, wherein said transparent glass substrate is a transparent glass plate having a high strain point. 13. The low-reflection glass article according to claim 8, wherein an electromagnetic wave shielding layer is provided on a surface opposite to the surface coated with the anti-reflection colored film. An optical filter for a plasma display panel, comprising: 14. 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.
14. The optical filter for a plasma display panel according to claim 13, having a transmission color represented by a chromaticity of 0. 15. A plasma display panel using the low reflection glass article according to any one of claims 8, 9, 10 and 12 as a front glass. 16. A step of applying a liquid composition for forming an antireflection film formed by dissolving a hydrolyzable / condensable metal compound in an organic solvent to the surface of a transparent glass substrate, and thereafter irradiating the surface of the coating with ultraviolet rays. The method according to any one of claims 1 to 12, comprising a step of repeating the application step and the ultraviolet irradiation step twice on the surface of the substrate on which the coating is applied. Method. 17. The metal compound is selected from titanium alkoxide, titanium halide or a compound selected from these chelates as a titanium raw material, and bismuth nitrate, bismuth oxyacetate, bismuth chloride, bismuth alkoxide as a bismuth raw material. Compound, cerium nitrate as a cerium raw material, a compound selected from cerium chloride, silicon alkoxide as a silica raw material,
The low-reflection glass article according to claim 16, which is at least one kind of a compound selected from an oligomer thereof, a hydrolyzed condensate thereof, and a gold compound or a gold colloid dispersion solution as a raw material of fine gold particles. Method.