KR20000065216A - Low-reflection glass article and its manufacturing method - Google Patents

Abstract

The present invention relates to a transparent glass substrate having a refractive index of 1.47 to 1.53, a first layer having a median refractive index (n ₁ ) of 1.60 to 1.95 and a film thickness of (60 to 130 nm) / n ₁ , and 1.91 to 2.60. And a second layer having a high refractive index (n ₂ ) and a film thickness of (140 to 230 nm) / n ₂ in a range of 0.20 or greater than the refractive index of the first layer described above, and a range of 1.35 to 1.59 A third layer having a low refractive index (n ₃ ) and a film thickness of (110 to 150 nm) / n ₃ having a value of 0.20 or more and smaller than the refractive index of the first layer described above is laminated in this order, The second layer contains a total of 70 mol% or more of titanium oxide and other metal oxides, and the third layer contains 50 to 100 mol% of silicon oxide and 0 to 10 mol% of the metal oxide in total. And the said 1st layer is a low reflection glass article containing 15-80 mol% of silicon oxide and 20-70 mol% of said metal oxides in total.

The low reflection glass article which coat | covered the optical multilayer film which can reduce a reflectance in the wide range of the visible light area by this invention can be provided.

Description

Low reflection glass article and its manufacturing method

Anti-reflective system using optical thin film to improve optical characteristics by reducing surface reflectance of optical parts such as cameras and glasses, or display parts of office automation (OA) electronic devices such as display panels, displays, and display filters. System is used. These antireflection films are required to have high transmittance along with low reflectivity in order to increase the visibility or to further enhance the optical characteristics originally provided.

The reduction of the reflectance by the optical thin film is due to the light interference effect. As for the three-layer optical multilayer film, for example, on the transparent glass substrate (refractive index 1.52), the first layer having an optical thin film having an intermediate refractive index (1.71) and a quarter wavelength, high refractive index (2.43) and two minutes A low reflection glass article is known in which a second layer having an optical thin film having a wavelength of 1 and a third layer having a low refractive index (1.39) and a third thin film having an optical thin film having a quarter wavelength are known in this order (for example, HKPulker, " Coatings on Glass ", p. 402-403, Amsterdam, Elsevier, 1984), it is known that the wavelength range of which the reflectance is close to zero can be enlarged and the reflection color can be improved at the same time.

On the other hand, plasma display panels (PDPs) have been put into practical use in recent years as wall-mounted televisions with large screens, and developments for further dissemination have been actively carried out. BACKGROUND ART A technique is known in which an optical filter having a multilayer anti-reflection film layer for preventing reflection of external light and an electromagnetic wave shielding layer and an optical filter for correcting the light 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, by dispersing a pigment that absorbs an excess of red components emitted by the PDP in a resin plate, thereby showing that the color tone that should be originally blue appears purple. On one surface of the substrate colored so as to be prevented, an antireflection film (which is formed by superimposing a plurality of films made of materials having different refractive indices on a plastic film substrate) is bonded with a transparent adhesive, and on the other surface of the transparent substrate, (1 ) A film that shields the line spectra of the electromagnetic wave and near-infrared region (e.g., sputtering silver-inorganic oxide fine particles on the PET film surface), and (2) an anti-interference film (e.g., fine unevenness on the outer surface of the transparent film) Formed so that the PDP is not in close contact with the PDP even in contact with the PDP. Published after the priority day of the present claimed invention the applicant has been known as disclosed in Japanese Patent Laid-Open No. Hei-9-306366.

However, referring to the optical thin film system which reduces the reflectance by using the above-described optical interference action, the equipment becomes large because each thin film is formed by using a vacuum system.

On the other hand, referring to the optical filter for PDP described above, there is a problem in that the production cost increases because the pigment is mixed in the resin plate and the antireflection film is stretched and attached to the surface thereof.

SUMMARY OF THE INVENTION The present invention has been made to solve such problems of the prior art, and an object of the present invention is to provide a low reflection glass article coated with an optical multilayer film capable of reducing reflectance in a wide range of visible light region without requiring large equipment. It is done.

In addition, the present invention is to solve the above-described prior art problem, to provide an antireflection colored film-coated glass article excellent in anti-reflection performance of visible light, moreover, can freely control the color tone of transmitted light, and high visible light transmittance, and Another object of the present invention is to provide an optical filter for PDP using the same.

The present invention provides a low reflection glass article and a method of manufacturing the same, and a low reflection glass article having a function of preventing reflection of visible light by coating an optical thin film on a surface of a low reflection glass article, particularly a transparent glass substrate. An optical filter using an article, and a plasma display panel.

BRIEF DESCRIPTION OF THE DRAWINGS It is a graph which shows an example of the preferable composition of the high refractive index film layer, the intermediate refractive index film layer, and the low refractive index film layer in this invention.

2 is a graph showing reflectance spectral characteristics of one embodiment of a low reflective glass article of the present invention.

EXAMPLE

Best Mode for Carrying Out the Invention

An Example is shown to the following and this invention is demonstrated to it further more concretely.

Preparation of High Refractive Index Film Solution Composition (H1 Liquid):

24.9 g of bismuth nitrate pentahydrate (bismuth raw material) was mixed with 118.6 g of 2-ethoxyethanol, 170.7 g of tetraisopropoxy titanium (titanium raw material) was added and stirred at 60 ° C for 3 hours. It cooled to room temperature and obtained the solution composition for high refractive index film formation (H1 liquid). During the H1 solution was contained titanium and bismuth, respectively, TiO _2, Bi ₂ O ₃ in terms of, respectively, 96 and 4 mol%.

Preparation of Low Refractive Index Film Solution Composition (L1 Liquid):

150 g of ethyl silicate ("ethyl silicate 40" manufactured by Gorcord Co., Ltd.) was mixed with 132 g of ethyl cellosolve, 18 g of 0.1 mol / L hydrochloric acid was added, and the mixture was stirred at room temperature for 2 hours (L1 solution).

Preparation of High Refractive Index Film Solution Composition (H2 Solution):

In terms of oxides by mixing a liquid H1 L1 liquid such that the amount of SiO ₂ is 10 mol%, a high refractive index to give a solution composition for film formation (H2 mixture). During H2 solution was containing silicon, titanium and bismuth are, respectively SiO _2, TiO _2, Bi ₂ O ₃ in terms of 10, 88.2 and 1.8 mol%, respectively.

Preparation of High Refractive Index Film Solution Composition (H3 Solution):

By the amount of SiO ₂ in terms of oxides mixed liquid H1 to L1 so that the liquid is 30 mol%, a high refractive index to give a solution composition for film formation (H3 liquid). Silicon, titanium, and bismuth contained 30, 68.6, and 1.4 mol% in terms of SiO ₂ , TiO ₂ , and Bi ₂ O ₃ , respectively, in the H 3 solution.

Preparation of the solution composition (M1 liquid) for intermediate refractive index film formation:

In terms of oxides SiO ₂ amount is by mixing a solution H1 to L1 so that the amount of 50 mol%, to give the intermediate-refractive index film forming solution composition (M1 liquid). In the M1 liquid, silicon, titanium and bismuth contained 50, 49 and 1 mol% in terms of SiO ₂ , TiO ₂ and Bi ₂ O ₃ , respectively.

Preparation of the solution composition (M2 liquid) for intermediate refractive index film formation:

In terms of oxides SiO ₂ amount is by mixing a solution H1 to L1 so that the amount of 70 mol%, to give the intermediate-refractive index film-forming composition solution (M2 liquid). In the M 2 liquid, silicon, titanium and bismuth contained 70, 29.4 and 0.6 mol%, respectively, in terms of SiO ₂ , TiO ₂ and Bi ₂ O ₃ .

Preparation of Low Refractive Index Film Solution Composition (L2 Solution):

In terms of oxides SiO ₂ amount is by mixing a solution H1 to L1 so that the liquid 90% by mole, to give a solution composition for forming low refractive index layer (L2 solution). In the L2 liquid, silicon, titanium, and bismuth contained 90, 9.8, and 0.2 mol%, respectively, in terms of SiO ₂ , TiO ₂ , and Bi ₂ O ₃ .

Preparation of High Refractive Index Film Solution Composition (H4 Solution):

1% of the gold chloride was dissolved in the H1 solution to obtain a solution composition for forming a high refractive index film having a coloring component (H4 solution).

Preparation of Low Refractive Index Film Solution Composition (L3 Liquid):

1% of the gold chloride was dissolved in L2 solution to obtain a solution composition for forming a low refractive index film having a coloring component (L3 solution).

Preparation of the solution composition (M3 liquid) for intermediate refractive index film formation:

It expressed by the weight% in M2 liquid, and dissolved 1% of gold chloride acid, and obtained the solution composition for low refractive index film formation which has a coloring component (M3 liquid).

[Examples 1-23, Comparative Examples 1-6]

Colorless transparent soda-lime glass plate (thickness: 1.1 mm, visible light transmittance: 91.2%, visible light reflectance (on the incident light side only 12 degrees incident): 4.03%, visible light reflectance (both surfaces, 12 degrees incident): 8.05 %, Respectively, represented by the chromaticity of the Lab table color system, transmitted light chromaticity a = -0.39, b = 0.2, transmitted light chromaticity ((a ² + b ² ) ^1/2 ) = 0.44, reflected light chromaticity a = 0.08, (同) b = -0.31, copper reflected light saturation ((a ² + b ² ) ^1/2 ) = 0.32, reflected light chromaticity (both surfaces) a = 0.02, copper b = -0.40, copper reflected light saturation ((a ² + b ² ) ^1/2 ) = 0.40) was washed with ultrasonic aqueous solution for 20 minutes, followed by ultrasonic irradiation in ultrapure water for 20 minutes, to obtain a substrate.

The above M1 liquid was applied to one surface of the substrate by a gravure coating method 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. A first layer film was formed. Subsequently, the above-mentioned H1 liquid was applied onto the first layer film, and ultraviolet rays were irradiated at the same distance, irradiation intensity, and irradiation time as described above using the above-described high pressure mercury lamp to obtain a second layer. Subsequently, above L2 liquid was apply | coated on this 2nd layer, ultraviolet-ray was irradiated on the same conditions as the above using said high pressure mercury lamp, and it was set as the 3rd layer. This was heated for 30 seconds in the electric furnace heated to 720 degreeC, and the low reflection glass plate which laminated | stacked the 1st layer film, the 2nd layer film, and the 3rd layer film in order on the board | substrate surface was obtained. The roll rotation speed by the gravure coating method of a 1st layer, a 2nd layer, and a 3rd layer was changed, and the various low reflection glass plates from which an optical film thickness differs were obtained (Examples 1-6, Comparative Examples 1-6).

In addition, the other thing which used H2 liquid instead of H1 liquid of the said 2nd layer liquid was performed similarly to Examples 1-6 (Examples 7-12). In addition, the other thing which used H3 liquid instead of H1 liquid of the said 2nd layer liquid was performed like Example 1 (Example 13). Instead of the first layer liquid M1 liquid and the second layer liquid H1 liquid described above in Examples 1 to 6, another one using M2 liquid and H3 liquid was performed in the same manner as in Examples 1 to 6 (Examples 14 to 16). In addition, the other thing which used L1 liquid as 3rd layer liquid was performed similarly to Examples 14-16 (Examples 17-23).

About the optical characteristic of the obtained low reflection glass plate, visible light reflectance _RVIS and visible light transmittance _TVIS were based on "JIS Z 8722", and the visible light reflectance was measured by the reflectance at 12 degree incidence. Here, the visible light reflectance of only the film surface (one side) with respect to the light incident from the film surface side is denoted by R (S) _VIS , and is a double-sided surface including reflection of the film surface and reflection on the back surface with respect to light incident from the film surface side. Visible light reflectance is denoted by R (D) _VIS . Regarding each layer of the first to third layers, the refractive index n is measured by ellipsometry on the refractive index value for light having a wavelength of 550 nm, and the film composition is shown in Table 2, and the refractive index (n) is expressed by Equation 6 The defined refractive index dispersion coefficient (v), film thickness (d) and optical film thickness (n _d ) are shown in Tables 3 and 4. The visible light reflectance R (S) _VIS only on the film surface and the chromaticity of the Lab table color system, and the reflected light chromaticity a, b and the reflected light saturation ((a ² + b) only on the film surface (one side) with respect to the light projected from the film surface side. ² ) ^1/2 ) Reflected light on both sides including the visible light reflectance R (D) _VIS on both sides including the back side and reflecting on the back side with respect to the light projected from the film surface side in Tables 5-6. Visible light transmittance T _VIS and transmission chromaticity a, when the values of chromaticities a, b and their reflected light saturation ((a ² + b ² ) ^1/2 ) are projected from Table 7 to Table 8 and from the film surface side, Each value of b and the transmitted light saturation ((a ² + b ² ) ^1/2 ) is shown in Tables 9 to 10, respectively. In addition, the visible light reflectance and the reflected light chromaticity of only the film surface (one surface) are the rough surface of the back surface (non-film surface) of the glass plate, and the black paint is applied and cured so that light reflection of the back surface does not occur. Measured.

Moreover, the spectral characteristic of the reflected light in the film surface at the time of making light inject from the film surface side with respect to the low reflection glass plate of Example 1 is shown in FIG. In the figure, the reflectances of the light at the wavelengths of 480 nm and 590 nm were all 0.01% or less, and the reflectances of the light at the 550 nm wavelength were found to be 0.13%.

As shown in Examples 1 to 23, the visible light reflectance R (S) _VIS at the film surface of the low reflection glass plate light incident from the film surface side of the present invention is 0.12 to 0.48%, which is 0.5% or less, and is an untreated glass substrate. It was found to be very small compared to 4.03% of the visible light reflectance (only the surface on the incident light side), and the effect of preventing visible light reflection was found to be large. On the other hand, in Comparative Examples 1-6 in which the film thickness of each film is out of range, the visible light reflectance R (S) _VIS of the film surface side is 1.04-1.91%, and the visible light reflectance of the untreated glass substrate (only the incident light surface) Although smaller than), it is considerably larger than the value of the embodiment.

The visible light reflectance R (D) _VIS on both surfaces including the back surface is also 4.09 to 4.47% in Examples 1 to 23, and is smaller than 8.05% of the untreated glass substrate. In addition, the saturation of the reflected light on both surfaces including the back surfaces of Examples 1 to 23 is in the range of 0.26 to 3.82, which is 5.0 or less, and the change from the value 0.40 of the untreated plate is very small and shows a reflected color close to neutral gray. have. The visible light transmittance T _VIS of Examples 1 to 23 was 92.3 to 93.8%, showing a value higher than the visible light transmittance T _VIS 91.2% of the untreated plate.

[Example 24]

M1 liquid, H1 liquid, and L2 liquid of Example 1 were similarly performed for the other ones substituted with M3 liquid, H4 liquid, and L3 liquid. The obtained low reflection glass showed the light gray hue of light gray, and the R (S) _VIS value was 0.11% and the T _VIS value was 90.2%.

Example and Comparative Example layer Use amount Film composition of each layer (mol%) SiO ₂ TiO ₂ Bi ₂ O ₃ Examples 1-6 First layer M1 liquid 50 49 One 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 One Examples 7-12 Second layer H2 liquid 10 88.2 1.8 Third layer L2 liquid 90 9.8 0.2 First layer M1 liquid 50 49 One Example 13 Second layer H3 liquid 30 68.6 1.4 Third layer L2 liquid 90 9.8 0.2 First layer M2 liquid 70 29.4 0.6 Examples 14-16 Second layer H3 liquid 30 68.6 1.4 Third layer L2 liquid 90 9.8 0.2 First layer M2 liquid 70 29.4 0.6 Examples 17-23 Second layer H3 liquid 30 68.6 1.4 Third layer L1 liquid 100 0 0

Example Visible light reflectivity (film surface) R (S) _VIS (%) Reflected light chromaticity (membrane) a b (a ² + b ² ) ^1/2 One 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 -10.03 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

Comparative Example Visible light reflectivity (film surface) R (S) _VIS (%) Reflected light chromaticity (membrane) a b (a ² + b ² ) ^1/2 One 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

Example Visible light reflectivity (both sides) R (D) _VIS (%) Reflected light chromaticity (both sides) a b (a ² + b ² ) ^1/2 One 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

Comparative Example Visible light reflectivity (film surface) R (D) _VIS (%) Reflected light chromaticity (both sides) a b (a ² + b ² ) ^1/2 One 4.96 0.15 -0.70 0.72 2 5.30 3.98 -6.14 7.32 3 5.63 4.90 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

Example Visible light transmittance T _VIS (%) Reflected light chromaticity a b (a ² + b ² ) ^1/2 One 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 0.06 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

Comparative Example Visible light transmittance T _VIS (%) Reflected light chromaticity a b (a ² + b ² ) ^1/2 One 92.3 -0.34 -0.22 0.40 2 91.6 -1.35 1.50 2.02 3 91.7 -1.45 -0.21 1.47 4 92.1 -0.28 -0.30 0.41 5 91.8 -0.56 -0.13 0.57 6 91.3 -0.97 1.26 1.59

[Examples 25-40, Comparative Examples 7-12]

Preparation of stock

2 mol of acetylacetone was dripped at 1 mol of titanium isopropoxide stirred in the flask by the dropping rod. This solution was used as a titanium oxide raw material. This contains 16.5 mol% of TiO ₂ .

6 g of 0.1 N hydrochloric acid and 44 g of ethyl cellosolve were added to 50 g of ethyl silicate (“ethyl silicate 40” manufactured by CORCODE), and stirred at room temperature for 2 hours. This solution was used as a silicon oxide stock solution. This can contain 20 mole% SiO _2.

Preparation of film forming solution composition

It counted the number from the glass substrate and used it as the coating liquid of the 1st layer, and it was set as the composition ratio shown in Table 11, and it manufactured with the intermediate refractive index film formation solution composition. A predetermined amount is mixed in the order of the titanium oxide stock solution, the solvent (ethyl cellosolve), the silicon oxide stock solution, and the gold (Au) raw material (gold chloride acid tetrahydrate), followed by stirring at room temperature for 2 hours to form an intermediate refractive index film (first layer). Solution composition coating liquids (M5-M20) were obtained. Similarly, it was set as the composition ratio shown in Table 12, and the high refractive index film (2nd layer) formation solution composition coating liquid (H5-H20) was obtained. Similarly, it was set as the composition ratio shown in Table 13, and the low refractive index film (3rd layer) formation solution composition coating liquid (L5-L20) was obtained.

The coating solution M5 prepared above was spin-coated for 15 seconds at a rotational speed of 3000 rpm on one surface of a soda lime silicate composition (refractive index = 1.52) having a thickness of 10 cm x 10 cm at a thickness of 1.1 mm. After air drying, it heat-treated at 550 degreeC for 2 minutes, and coat | covers an intermediate refractive index film, Then, the coating liquid H5 prepared above was spin-coated for 15 second at 2000 rpm, and after air drying, it heat-treated at 550 degreeC for 2 minutes, and high refractive index coloring was carried out. The membrane was coated. Further, the coating liquid L5 prepared above was spin-coated for 15 seconds at a rotational speed of 2000 rpm for 15 seconds, followed by heat treatment at 550 ° C. for 2 minutes, followed by a first layer having the composition, refractive index, film thickness, and optical film thickness shown in Table 14, respectively. Intermediate refractive index film, a high refractive index film of the second layer each having a composition, refractive index, film thickness and optical film thickness shown in Table 15, and a coloring low having a composition, refractive index, film thickness and optical film thickness shown in Table 16, respectively. A glass plate coated with a refractive index film was obtained (Example 25). The visible light reflectance R _VIS of this glass plate reflects only the film surface ("R _VIS film surface") that enters the D light source light at an angle of 12 degrees from the film surface coated with the colored film and blocks the reflected light from the back surface (non-film surface). ) And reflectance ("R _VIS double-sided") including two reflections from the back side and the membrane surface side were measured. The visible light transmittance T _VIS (D light source) was measured according to JIS R 3106 and the JIS Z 8729 regarding the chromaticity of the transmitted light.

The measurement results, the visible light transmittance (T _VIS), and the JS color, the visible light reflectance of tugwagwa (R _VIS film surface, and both surfaces R _VIS) were as shown in Table 17. In addition, the obtained colored film showed favorable results in chemical resistance and friction resistance. In addition, when the said anti-reflective colored film is coat | covered on both surfaces of the said glass substrate, the reflectance ("R- _VIS both-sides") containing reflection from the surface side and the back side, the anti-reflective colored film is a surface of one side of a glass substrate. It was 1.2% smaller than the reflectance ("R _VIS both surfaces") 3.0% at the time of coating on the bay.

Similarly, using the coating liquids (M6 to M20, H6 to H20 and L6 to L20) shown in Tables 11 to 13, an intermediate refractive index film having the composition, refractive index, and film thickness as shown in Tables 14 to 16, respectively, An anti-reflective colored film-coated glass article (Examples 26 to 40) coated with a high refractive index film and a low refractive index film was obtained. The measurement results for these optical properties are summarized in Table 17.

As shown in Examples 25 to 30 and Examples 34 to 36, the red color was absorbed and the transmission color was represented by a cyan color, that is, a Lab color system, where a = -8.4--1.1 and b =-7.8--1.2. And the antireflection film-coated glass article having a reflectance (“R _VIS film surface”) only at the film surface side of 0.5% or less. Further, as shown in Examples 31 to 33, yellow was absorbed and the transmission color was blue-violet, i.e., the Lab color system, with a = 0.3 to 0.8 and b = -10.5 to -3.5. The antireflection film-coated glass article having a "" R _VIS film surface ") 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, it is represented by Lab color system, and has a transmitted light chromaticity of a = 2.5 to 9.8 and b = -5.3 to -0.8, and only on the membrane surface side. The antireflective film-coated glass article having a visible light reflectance (“R _VIS film surface”) of 0.5% or less was obtained. And the antireflective film-coated glass articles of all of Examples 25-40 showed 60% or more of visible light transmittance (T _VIS ).

Using the coating liquid shown in Table 18, to adjust the rotation speed in spin coat which is the application | coating conditions of the coating liquid for high refractive index film formation, the coating liquid for intermediate refractive index film formation, or the coating liquid for low refractive index film formation. As shown in Table 19, the antireflective colored film-coated glass articles (Comparative Examples 7-12) were prepared in the same manner as in Example 29 except that the film thicknesses of the high refractive index film, the intermediate refractive film, or the low refractive film were changed. Got it. The measurement result about these optical characteristics is as showing in Table 20. In the comparative example, the visible light reflectance ("R _VIS film surface") only at the film surface side was 3.0 to 4.2%, and the visible light reflection prevention performance was clearly inferior to that of the R _VIS film surface (0.1 to 0.3%) of the embodiment.

1st layer coating liquid composition Example Coating liquid Titanium oxide Silicon oxide Au raw material menstruum number number 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 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-M20 10.0 16.8 0 73.2 41 M21 11.0 18.4 0 70.6

2nd layer coating liquid composition Example Coating liquid Titanium oxide Silicon oxide Au raw material menstruum number number Stock solution (g) Stock solution (g) (g) (g) 25-33 H5 to H13 30.3 0 0 69.7 34 H14 23.3 0 2.0 74.7 35 H15 25.8 0 1.3 73.0 36 H16 27.9 0 0.7 71.4 37-40 H17 ~ H20 30.3 0 0 69.7 41 H21 42.4 0 0 57.6

3rd layer coating liquid composition Example Coating liquid Silicon oxide Au raw material menstruum number number Stock solution (g) (g) (g) 25-36 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 0.3 75.7 41 L21 28.8 0.4 70.8

Example Medium refractive film composition (mol%) Refractive index Film thickness n ₁ d number TiO ₂ SiO ₂ Au n 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 95 27 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 93 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 1.76 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

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 0 0 2.20 85 187 26 100 0 0 2.20 84 185 27 100 0 0 2.20 84 185 28 100 0 0 2.20 84 185 29 100 0 0 2.20 85 187 30 100 0 0 2.20 84 185 31 100 0 0 2.20 84 185 32 100 0 0 2.20 85 187 33 100 0 0 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 0 0 2.20 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

Example Low refractive index film composition (mol%) Refractive index Film thickness n ₃ · d number SiO ₂ Au n ₃ d (nm) (nm) 25 100 0 1.46 81 118 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 39 97.4 2.6 1.46 83 121 40 98.7 1.3 1.46 82 120

Example T _VIS Chromaticity of transmitted light R _VIS (%) number (%) a b Prevent both sides 25 66.2 -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 3.3 35 81.0 -4.6 -2.3 0.2 3.5 36 91.0 -2.3 -1.2 0.3 3.7 37 76.8 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

Comparative example layer Use amount Film composition of each layer (mol%) Ti0 ₂ SiO ₂ Au First layer M9 liquid 26.9 70.3 2.8 7-12 Second layer H9 liquid 100 0 0 Third layer L9 liquid 0 100 0

Comparative Example First layer Second layer Third layer Refractive index Thickness n ₁ d Refractive index Thickness n ₂ · d Refractive index Thickness n ₃ · d 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

Comparative example T _VIS Chromaticity of transmitted light R _VIS (%) number (%) a b Prevent both sides 7 78.0 -0.9 -3.4 3.0 6.3 8 75.2 -0.7 -3.3 4.0 7.1 9 76.9 -0.3 -3.9 3.2 6.6 10 74.0 -0.2 -3.1 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]

Coating liquid M21 having a composition shown in Table 11 on one surface of a non-colored float glass plate (distortion point 575 ° C.) having a high distortion point of 59 mm x 89 cm by 3.2 mm thickness after polishing and cleaning the surface with cerium oxide abrasive. Was coated, and a first layer film was formed by irradiating ultraviolet light for 30 seconds at an irradiation intensity of 15 mW / cm ² at a distance of 10 cm using a high-pressure mercury lamp of 160 W / cm. Subsequently, coating liquid H21 having the composition shown in Table 12 was applied onto this first layer film, and ultraviolet irradiation for 30 seconds was performed at a irradiation intensity of 15 mW / cm ² at a distance of 10 cm using a high-pressure mercury lamp of 160 W / cm. To form a second layer film. Furthermore, the coating liquid L21 which has the composition shown in Table 13 was apply | coated on this 2nd layer film, it heated in glass conveyance 250 degreeC by the conveyor conveyance type ultraviolet heating furnace (300 degreeC in furnace furnace), and the intermediate | middle refractive index film of a 1st layer An antireflection film composed of two layers of high refractive index film and a third layer of colored low refractive index film was formed on the surface of the glass plate.

As a light shielding layer, black ink is printed by silk screen printing on the periphery (about 10 mm in width) of the surface (first surface) opposite to the surface (first surface) on which the anti-reflective film of this glass plate was formed. An electroconductive silver paste was printed as an earth electrode on the black printing layer, and it baked at 500 degreeC. Then, a multi-layered film of silver was formed on the entire surface of this surface (second surface) as the electromagnetic shielding layer by the sputtering method. If the silver multilayer film is formed on one surface of a non-colored float glass plate on which no anti-reflection film is formed, the transmission color tone (chromaticity) is represented by a Lab color system, where a = -2.4, and b = 0.7. And yellow-green color. In the case where the glass plate having the anti-reflection film formed on the first face and the electromagnetic wave shielding layer on the second face is closely arranged so that the electromagnetic wave shielding layer faces the PDP, in order not to generate a Newton ring, which is an interference ring, and As a shatterproof film in the case of being damaged, a plastic film (Anti-glare film) having fine irregularities formed on its surface was stretched and pasted on the electromagnetic wave shielding layer on the second surface of the glass plate, thereby obtaining an optical filter for PDP. The transmission color tone of the obtained optical filter was a = 0.2, b = 0.3, and showed neutral gray.

EXAMPLE 42

A commercially available antireflection film-compatible antireflection film (multiple layers of films made of materials with different refractive indices overlapped and deposited) instead of being stretched and pasted with a plastic film having minute unevenness formed on the surface thereof in Example 41 ) Was stretched and pasted to the second surface of the glass plate, to obtain an optical filter for PDP. The optical properties were almost the same as in Example 41.

[Industry availability]

As described above, as described 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 the film surface is obtained. Moreover, according to this invention, the anti-reflective performance of visible light is excellent, Furthermore, the color tone of transmitted light can be controlled freely, The anti-reflective coloring film coating glass article with high visible light transmittance, and the optical filter for PDP using the same are obtained.

The present invention provides a first layer having a median 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, and a range of 1.91 to 2.60. A second layer having a high refractive index (n ₂ ) and a film thickness of (140 to 230 nm) / n ₂ of at least 0.20 compared to the refractive index of the first layer described above, and within the range of 1.35 to 1.59 the refractive index of at least 0.20, a value less than the refractive index of the one first layer (n ₃₎ and (110~150 nm) / n third layer having a film thickness of _3, low-reflective glass, which is three-layer laminated in this order Goods.

The present invention further provides a total of 70 mol% or more of the at least one metal oxide selected from the group consisting of titanium oxide, cerium oxide, bismuth oxide, zirconium oxide, niobium oxide, and tantalum oxide. One third layer contains 50 to 100 mol% of silicon oxide, 0 to 10 mol% of the metal oxide in total, and the first layer contains 15 to 80 mol% of silicon oxide It is a low reflection glass article containing 20-70 mol% of one metal oxide in total.

The present invention is described in detail below.

In the present invention, the refractive index (refractive index) of the first layer (medium refractive index film), the second layer (high refractive index film), and the third layer (low refractive index film) laminated in order on the transparent substrate having a refractive index of 1.47 to 1.53 is Unless otherwise specified, it is defined as a value for light having a wavelength of 550 nm. The same applies to n ₁ , n ₂ , and n ₃ , respectively, and the refractive index value (n ₁ ) of the first layer (intermediate refractive film) is defined. The range is 1.60 to 1.95, the refractive index value n ₂ of the second layer (high refractive index film) is 1.91 to 2.60, and is at least 0.20 larger than the refractive index of the first layer described above, and the third layer (low The refractive index value n ₃ of the refractive index film) is in the range of 1.35 to 1.59 and is at least 0.20 smaller than the refractive index of the first layer.

The refractive indices are preferably selected so as to almost satisfy the relationship of the following formula (1), that is, the right side value of the following formula (1) reaches 95 to 110% of the left side value. In other words, the refractive index value of the first layer, the refractive index values of the (middle refractive index layer) (n _1), second layers the refractive index value of the (high-refractive-index film) (n ₂₎ and the third layer (low refractive film) (n ₃₎ It is preferable that the following formula (2) is satisfied.

n ₂ × n ₃ = n ₁ ² (1)

0.95 × n ₂ × n ₃ ≤ n ₁ ² ≤ 1.10 × n ₂ × n ₃ (2)

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

By doing in this way, the reflectance in the film surface side surface of the light of the specific wavelength incident from the film surface side can be made substantially zero.

The difference degree of the refractive index of each film | membrane by a difference of an optical wavelength is defined as refractive index dispersion coefficient (nu) as shown in following formula (3).

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.

Preferable ranges of the refractive index dispersion coefficients v 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 12, and 50 or more, respectively. If the refractive index dispersion coefficient v of each layer is out of the above range, it becomes difficult to achieve the purpose of small visible light reflection. Table 1 summarizes the ranges of refractive index, optical film thickness, and refractive index dispersion coefficient v of these first to third layers. By selecting such a refractive index, optical film thickness, and dispersion coefficient, a low reflection glass article having a visible light reflectance (film surface) of 0.5% or less, more preferably 0.3% or less is obtained.

Refractive index Film thickness (nm) Refractive index dispersion coefficient ν First layer 1.60-1.95 (= n ₁ ) (60 to 130) / n ₁ 13-30 Second layer 1.91-2.60 (= n ₂ ) (140-230) / n ₂ 2-12 Third layer 1.35-1.59 (= n ₃ ) (110 to 150) / n ₃ 50 or more

The high refractive index film (second layer) according to the present invention includes the periodic table IB group (Cu, Ag, Au), the IIA group (Be, Mg, Ca, Sr, Ba, Ra), the IIB group (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, Ta, 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, Pd, Os, Ir, At least one selected from titanium (Ti), cerium (Ce), bismuth (Bi), zirconium (Zr), niobium (Nb), and tantalum (Ta) among oxide candidates of Pt, Pu, Am, and Cm elements. The metal oxide is a main component. These metal oxides are respectively 70 mol%, preferably 80 mol%, more preferably in terms of TiO ₂ , CeO ₂ , Bi ₂ O ₃ , ZrO ₂ , Nb ₂ O _5, and Ta ₂ O ₅ . 90 mol%. As other components below 30 mol%, a silicon oxide and the coloring component mentioned later are mentioned.

The low refractive index film (third layer) according to the present invention contains 50 to 100 mol% of silicon oxide (silica), and further comprises titanium (Ti), cerium (Ce), bismuth (Bi), zirconium (Zr), and niobium ( Nb) and at least one metal oxide selected from decarburization (Ta) are converted into TiO ₂ , CeO ₂ , Bi ₂ O ₃ , ZrO ₂ , Nb ₂ O _5, and Ta ₂ O ₅ , respectively, and the total is 0. It contains-10 mol%. As the oxide of the metal, one of the same kind as the metal oxide contained in the high refractive index film described above can be selected. By selecting in this way, the shrinkage coefficient in the hardening process of the layer of a low refractive index film and the layer of a high refractive index film | membrane approximates, and it becomes difficult to produce a crack and a film peeling. Moreover, the adhesiveness in the interface of a low refractive index film layer and a high refractive index film layer can be improved. In the case where the above-mentioned high refractive index film contains various kinds of metal oxides, for example, two kinds of titanium oxide and bismuth oxide, titanium oxide and bismuth are almost equal to the ratio of titanium oxide and bismuth oxide contained in the high refractive index film. It is preferable to contain an oxide in the low refractive index film described above. As a component which may be contained other, the coloring component mentioned later is mentioned.

The intermediate refractive index film (first layer) according to the present invention contains 15 to 80 mol% of silicon oxide, and further includes titanium (TI), cerium (Ce), bismuth (Bi), zirconium (Zr), and niobium (Nb). And at least one metal oxide selected from decarburization (Ta), respectively, in terms of TiO ₂ , CeO ₂ , Bi ₂ O ₃ , ZrO ₂ , Nb ₂ O _5, and Ta ₂ O ₅ , which are 20 to 70 in total. It contains mol%. As this metal oxide, the same kind of metal oxide contained in the above-mentioned high refractive index film can be selected. By selecting in this way, the shrinkage coefficient in the hardening process of a middle refractive index film layer and a high refractive index film layer becomes approximated, and a crack and a film peeling hardly occur. Moreover, the adhesiveness in the interface of an intermediate refractive index film layer and a high refractive index film layer can be improved. As one preferable example of the intermediate refractive index film (first layer), the liquid refractive index film (second layer) and the respective liquid compositions forming the low refractive index film (third layer) of the present invention are mixed at an arbitrary ratio. Membranes formed using liquid compositions can be exemplified.

The coloring component may be contained in at least one layer of the high refractive index film, the low refractive film, and the intermediate refractive film in the present invention. As such a coloring component, the metal ultrafine particle which consists of 1 type (s) or 2 or more types chosen from group IB, group VIII of a periodic table is mentioned. Among these, preferable examples include noble metals such as gold (Au), platinum (Pt), palladium (Pd), rhodium (Rh) and silver (Ag), and particularly preferred gold. It is preferable to contain 0.5-20 mol% of these coloring component metal microparticles | fine-particles.

Titanium oxide, bismuth oxide, and silicon oxide as one specific form of each optical thin film of a high refractive index film (2nd layer), an intermediate refractive film (1st layer), and a low refractive index film (3rd layer) in this invention. The film containing these can be illustrated. This film will be described below.

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

The ratio of titanium oxide and bismuth oxide in the high refractive index film containing the titanium oxide, bismuth oxide and silicon oxide of the present invention is preferably selected so that the refractive index of the film is maximized. The content of titanium oxide and bismuth oxide in the thin film is expressed in molar ratio assuming that the oxidation states of titanium and bismuth are TiO ₂ and Bi ₂ O ₃ , respectively, and Bi ₂ O ₃ to the sum of TiO ₂ and Bi ₂ O _3. The ratio, i.e., Bi ₂ O ₃ / (TiO ₂ + Bi ₂ O ₃ ) is preferably 1 to 96%, more preferably 2 to 60%, and still more preferably 3 to 50%.

The content of titanium oxide, bismuth oxide, and silicon oxide in the high refractive index film is TiO ₂ , Bi ₂ O _{3, in the} TiO ₂ -Bi ₂ O ₃ -SiO ₂ based ternary composition, as shown in FIG _. The molar ratio of SiO ₂ is represented by coordinate points (TiO ₂ , Bi ₂ O _{3, and} mole% of SiO ₂ ), so that A (69, 1, 30), B (99, 1, 0), C (5, 95, 0), D (3, 67, 30) is required to be a ratio within the range of the rectangle ABCD, preferably E (78, 2, 20), F (98, 2, 0), G (40, 60, 0), the ratio within the range of the square EFGH consisting of H (32, 48, 20), more preferably I (87, 3, 10), J (97, 3, 0), K (50, 50 , 0) and the ratio within the range of the square IJKL consisting of L (45, 45, 10).

A high refractive index film having a refractive index of 2.06 or more is obtained in the range of the titanium oxide, bismuth oxide, and silicon oxide in the high refractive index film within the range of the rectangular ABCD, and similarly within the range of the refractive index of 2.18 or more and the rectangular IJKL within the range of the rectangular EFGH. A high refractive index film having a refractive index of 2.30 or more is obtained. In the case where the optical thin film containing titanium oxide, bismuth oxide and silicon oxide is used as the high refractive index film in this way, components other than the above components, such as cerium oxide, zirconium oxide, decarburized oxide, niobium, if the refractive index cannot be reduced to that level Oxides, tungsten oxides, antimony oxides and the like may be contained in small amounts, for example, 10% or less.

On the other hand, when using an optical thin film containing titanium oxide, bismuth oxide and silicon oxide as the low refractive index film in the present invention, the content of silicon oxide is preferably 70 mol% or more in terms of mol% of SiO ₂ . And a more preferable ratio is 80 mol% or more, and a still more preferable ratio is 90 mol% or more.

The content rate of titanium oxide, bismuth oxide, and silicon oxide in this low refractive index film is shown similarly to the case of a high refractive index film, as shown in FIG. 1, and Y (0, 0, 100), Z (29.5, 0.5, 70) , A '(1.5, 28.5, 70) must be in the ratio of the range of the triangle YZA', Y (0, 0, 100), B '(19.5, 0.5, 80), C' (8, 12 It is preferable that it is the ratio within the range of the triangle YB'C 'which consists of 80, More preferably, Y (0, 0, 100), D' (9.5, 0.5, 90), E '(5, 5, 90) Is the ratio within the range of the triangle YD'E '.

When an optical thin film containing titanium oxide, bismuth oxide and silicon oxide is used as the intermediate refractive index film (first layer), the content rate of titanium oxide, bismuth oxide and silicon oxide in the thin film is as shown in FIG. In the same manner as in the case of the high refractive index film, it is within the range of the rectangular MNOP consisting of M (30.5, 0.5, 69), N (68, 1, 31), O (3.5, 65.5, 31), and P (1.5, 29.5, 69). It is necessary to set the ratio, and the ratio within the range of the rectangular QRST consisting of Q (39, 1, 60), R (58.5, 1.5, 40), S (24, 36, 40), and T (16, 24, 60). Preferably, the range of rectangular UVWX consisting of U (43, 2, 55), V (53, 2, 45), W (27.5, 27.5, 45), X (22.5, 22.5, 55) It is the ratio within. A high refractive index film having a refractive index of 1.70 to 2.05 is obtained in the range of the content of titanium oxide, bismuth oxide, and silicon oxide in the medium refractive index film in the range of rectangular MNOP. Similarly, within the range of rectangular QRST, a refractive index of 1.80 to 2.00, rectangular UVWX Within this range, an intermediate refractive index film having a refractive index of 1.85 to 1.95 is obtained.

Titanium oxide and bismuth oxide in each film in the case where the optical thin film containing the 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 film (first layer) It is preferable to make a ratio approximate the ratio of the titanium oxide and bismuth oxide in the high refractive index film (2nd layer) to laminate | stack. By doing in this way, the difference of the thermal contraction rate of the intermediate | middle refractive index film and the high refractive index film, and the difference of the thermal contraction rate of the high refractive index film and the low refractive index film at the time of baking can become small, and it can prevent a crack and an interface peeling. Moreover, wavelength dispersion of the refractive index of the high refractive index film, the low refractive index film, and the intermediate refractive film is approximated, and optical characteristics such as transmitted light color tone, reflected light color tone, and visible light reflectance in the low reflection glass formed by laminating using these optical thin films This is improved.

As another specific form of the low reflection glass article in this invention, a high refractive index film (2nd layer) contains a titanium oxide, an intermediate refractive film (1st layer) contains a titanium oxide and a silicon oxide, and low refractive index The film (third layer) contains silicon oxide, and the gold fine particles are contained in at least one of a high refractive index film (second layer), an intermediate refractive film (first layer), and a low refractive index film (third layer). The case can be illustrated. It demonstrates below.

Each component of the intermediate refractive index film (first layer) of the antireflection film of the present invention will be described below. Silicon oxide (Si oxide) is an essential component for adjusting the refractive index of a film, and when the content is low, the refractive index of a film becomes high. On the contrary, even when there is much content, refractive index will become low. The content of silicon oxide is, and 15-80% by mole in terms of SiO _2, preferably 30~78 mol%, more preferably 35-74% by mole. Titanium oxide is necessary to increase the refractive index of the film. When the content is low, the refractive index of the film decreases, and when the content is large, the film has a large refractive index. The content of titanium oxide is 20 to 70% by mole in terms of TiO _2, preferably 22~65 mol%, more preferably 25-60% by mole. When the thickness of the intermediate refractive index film is too thin, the antireflection effect is lowered. On the contrary, when the thickness is thick, the antireflection effect is lowered, and cracks are formed, resulting in a decrease in film strength. It is -55 nm, More preferably, it is 47-53 nm. When the refractive index of the intermediate refractive index film is lowered, the antireflection effect is not sufficiently obtained. Therefore, it is preferably 1.60 to 1.90, more preferably 1.65 to 1.85, and even more preferably 1.70 to 1.80.

Each component of said high refractive index film (2nd layer) in this invention is demonstrated below. Titanium oxide is necessary for film formation of the film and for increasing the refractive index of the film. When the content is low, the refractive index of the colored film becomes low. In addition, when the content is large, the refractive index of the film becomes large. The content of titanium oxide in terms of the TIO ₂ is 70-100% by mole, preferably 80 to 100% by mole, and more preferably 88-100% by mole. The content of silicon oxide is, in terms of SiO ₂ and 0 - 30% by mole, preferably 0 to 20 mol%, and that, more preferably 0-12% by mole.

If the thickness of the high refractive index film is too thin, the anti-reflection effect is lowered. On the contrary, even if it is thick, the anti-reflection effect is lowered, and since cracks are formed, the film strength is lowered. 95 nm, More preferably, it is 80-90 nm. When the refractive index of the film is lowered, the antireflection effect is not sufficiently obtained, and therefore it is preferably 1.91 to 2.30, more preferably 1.96 to 2.30, and even more preferably 2.01 to 2.30.

Each component of said low refractive index film (third layer) in this invention is demonstrated below. Silicon oxide is necessary to make a film or to lower the refractive index of the film. When the content is low, the film has a high refractive index. In addition, when the content is large, the refractive index of the film becomes small. The content of silicon oxide is 85-100% by mole in terms of SiO _2, and more preferably 90-100% by mole.

When the thickness of the low refractive index film is too thin, the antireflection effect is low, and on the contrary, even if it is thick, the antireflection effect is low, and since cracks are formed, the film strength is lowered. Therefore, the thickness is 65 to 105 nm, and preferably 75 to 95 nm, More preferably, it is 80-90 nm. Since the antireflection effect is not sufficiently obtained when the refractive index of the film is lowered, the film is 1.35 to 1.59, preferably 1.35 to 1.50, and more preferably 1.35 to 1.47.

Gold is a coloring fine particle which gives a color to a high refractive index film, an intermediate refractive film, or a low refractive film. If the content is too low, sufficient coloring will not be obtained. On the contrary, if the content is too high, the durability of the film will decrease, or excess gold fine particles will come out of the film. Therefore, content of gold microparticles | fine-particles is 0.5-20 mol%, Preferably it is 1-15 mol%, More preferably, it is 1-11 mol%.

As a method of forming a high refractive index film, a low refractive film, and an intermediate refractive film in this invention, although it can form by the sputtering method, the CVD method, and the spray pyrolysis method, it is preferable by the sol-gel method from a cost point of view. As the coating by the sol-gel method, a spin coating method, a dip coating method, a flow 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, the low refractive index film, and the intermediate refractive film in the present invention are formed by a sol-gel method, for example, an optical thin film containing titanium oxide, bismuth oxide, silicon oxide and gold fine particles, the coating liquid composition is It is obtained by dissolving a metal compound capable of hydrolyzing and condensing 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 gold fine particle material in an organic solvent.

As a titanium compound. Titanium alkoxides, titanium alkoxide chlorides, titanium chelates and the like are used. As titanium alkoxide, titanium methoxide, titanium epoxide, titanium n-propoxide, titanium isoprooxide, titanium n-butoxide, titanium isobutoxide, titanium methoxy propoxide, titanium stearyl oxide, Titanium 2-ethyl hexoxide and the like. Titanium chloride triisopropoxide, titanium dichloride diethoxide, etc. are mentioned as titanium alkoxide chloride. Examples of titanium chelates include titanium triisopropoxide (2,4-pentanedionate), titanium diisopropoxide (bis-2,4-pentanedionate), titanium arylacetate triisopropoxide and titanium bis (Triethanolamine) diisopropoxide, titanium di-n-butoxide (bis-2,4-pentanedionate) and the like are used.

As a bismuth compound, bismuth nitrate, bismuth acetate, bismuth oxyacetic acid, bismuth chloride, bismuth alkoxide, bismuth hexafluoropentadionate, bismuth t-pentoxide, bismuth tetramethylheptanedionate, etc. are used. As the cerium compound, cerium nitrate, cerium chloride or the like is used.

As a silicon compound, what mixed silicon alkoxide with solvents, such as alcohol, and advanced hydrolysis and superposition | polymerization with an acidic or basic catalyst is used. As the silicon alkoxide, silicon methoxide, silicon ethoxide or oligomers thereof are used. As the acid catalyst, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, trichloroacetic acid, trifluoroacetic acid, phosphoric acid, fluoric acid, formic acid, and the like are used. As the basic catalyst, ammonia and amines are used.

Examples of the fine particles of gold fine particles include chloroacetic acid tetrahydrate, chloroacetic acid trihydrate, sodium chlorate dihydrate, gold cyanide, potassium cyanide, gold diethylacetylacetonate complex, or gold colloid dispersion solution. Can be mentioned.

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 nitrate, chloride, sulfate, and the like can also be used, but cerium nitrate and cerium acetylacetonate are preferred from the viewpoint of stability and availability.

Examples of zirconium compounds include tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, tetra n-propoxy zirconium, tetraisopropoxy zirconium isopropanol complex, tetraisobutoxy zirconium, tetra n-butoxy zirconium and tetra sec-butoxy zirconium, tetra t-butoxy zirconium, and the like can be preferably and conveniently used. Moreover, the alkoxide of zirconium halides, such as a zirconium monochloride trialkoxide and a zirconium dichloride dialkoxide, can also be used. Moreover, the zirconium alkoxide which chelated the said zirconium alkoxide with the (beta) -keto ester compound is also used suitably. As a chelating agent, CH ₃ COCH ₃ COOR (where R is CH ₃ , C ₂ H ₅ , C ₃ H ₇ or C ₄ H ₉ ), such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, and butyl acetoacetate Acetoacetic acid esters represented by the above can be enumerated, and among them, acetoacetic acid alkyl esters, especially methyl acetoacetate and ethyl acetoacetate, can be obtained at a relatively low price. Although the degree of chelation of zirconium alkoxide may be part or all, it is preferable to chelate at a molar ratio of (β-ketoester) / (zirconium alkoxide) = 2 because the chelate compound becomes stable. Zirconium alkoxides chelated with chelating agents other than the β-ketoester compound, for example, acetylacetone, are insoluble in solvents such as alcohols, and thus are precipitated and cannot be applied to the coating solution. Furthermore, it is also possible to use alkoxy zirconium organic acid salts in which at least one of the alkoxy groups of the zirconium alkoxide is substituted with organic acids such as acetic acid, propionic acid, butanoic acid, acrylic acid, methacrylic acid and stearic acid.

As the niobium compound, niobium chloride, niobium pentaethoxide, or the like is used. In addition, niobium trimethoxydichloride produced by dissolving niobium contaminated in methyl alcohol, niobium triethoxydichloride produced by dissolving in ethyl alcohol, niobium triisopropoxydichloride produced by dissolving in isopropyl alcohol, and the like. It can be illustrated. Furthermore, niobium triethoxyacetylacetonate produced by adding acetylacetone to niobium pentaethoxide, niobium ethoxydiacetylacetonate, or niobium triethoxyethylacetonate produced by adding ethyl acetoacetate to niobium pentaethoxide And niobium ethoxydiethylacetonate can be illustrated.

As a tantalum compound, tantalum methoxide, tantalum pentaethoxide, tantalum penta n-butoxide, tantalum tetraethoxide deacetylacetonate, etc. are mentioned.

The organic solvent used in the coating liquid composition used for the formation of the above high refractive index film and the low refractive index film, although depending on the coating method, methanol, ethanol, isopropanol, butanol, hexanol, octanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, propylene glycol monomethyl ether, propylene glycol monoethyl glycol, cellosolve acetate, ethylene glycol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, hexylene glycol, di Ethylene glycol, tripropylene glycol, polypropylene glycol, diacetone alcohol, etc. are mentioned. The coating liquid composition may be used alone or in plural in order to adjust the viscosity, surface tension and the like of the coating liquid. Moreover, you may add a small amount of a stabilizer, a leveling agent, a thickener, etc. as needed. The amount of solvent used depends on the finally obtained high-refractive-index film, intermediate-refractive-index film and low-refractive-index film thickness, and the coating method employed, but is usually used so that the total solid content falls within the range of 1 to 20%.

After apply | coating said coating liquid composition by the said application | coating method, it heat-fires at the temperature of drying and / or 250 degreeC or more, and then repeats, and repeats the process of apply | coating the next coating liquid on it, and drying and / or heat baking process Thereby, the ultraviolet ray heating reflective glass article is completed. The film thus obtained has excellent performances such as transparency, environmental resistance, scratch resistance, and the like, and is easily generated due to the difference in thermal shrinkage in the densification process of the high refractive index film layer, the intermediate refractive film film layer, and the low refractive film film layer even after lamination. Film peeling and crack formation can be suppressed.

Instead of the manufacturing method which utilizes drying / baking by said drying and / or 250 degreeC or more heating, the light irradiation method described next can also be used. In other words, the coating-coating composition is applied by the coating method described above, and then the step of irradiating the coating film with an electromagnetic wave having a wavelength shorter than visible light is performed, followed by the step of applying the next coating liquid. It is a method of repeating a drying process.

Examples of electromagnetic waves having a wavelength shorter than that of visible light include gamma rays, X rays, and ultraviolet rays, but ultraviolet irradiation is preferable from the practical point of view of the device in consideration of irradiation to a gas having a large area. As the ultraviolet light source, an excimer lamp, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp and the like are used. 10 mW / cm ² or more, preferably 50 mW / cm ² or more, more preferably 100 mW / cm ² , using a high-pressure mercury lamp that emits 254 nm and 303 nm efficiently with 365 nm as the main wavelength It is preferable to irradiate a coating film with the above irradiation intensity. The coating film which apply | coated the irradiation energy of 100 mJ / cm <^2> or more, Preferably it is 500 mJ / cm <^2> or more, More preferably, 1000 mJ / cm <^2> or more using the coating liquid composition of this invention using such an ultraviolet light source. Apply to cotton. After repeating application and ultraviolet irradiation by the required number of layers, heating is performed for 10 seconds to 2 minutes in a furnace heated to 500 to 800 ° C as necessary. Thereby, the laminated | multilayer film which is excellent in performance, such as transparency, environmental resistance, and abrasion resistance at low temperature, and is hard to produce a crack is provided.

It is also possible to simultaneously perform drying and / or firing by heat while irradiating ultraviolet rays. By simultaneously using the drying method by ultraviolet irradiation and the drying process by thermal drying at the temperature of preferably 250 degrees C or less simultaneously, the coating film excellent in performance, such as transparency, environmental resistance, and abrasion resistance, is provided, and lamination | stacking is repeated. Even if the high refractive index film layer, the intermediate refractive index film layer, and the low refractive index film layer are densified in the heat shrinkage difference in the process of densification, film peeling and crack formation that are likely to occur can be suppressed. By using ultraviolet irradiation in this way, the drying process can be speeded up and productivity can be dramatically increased.

As the glass substrate according to 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, colored with green, bronze, or the like, or blocking ultraviolet rays or heat rays A glass plate or the like may be used, and an automotive glass plate and a display glass plate having a thickness of 0.5 mm to 5.0 mm are preferably used, and the above-described laminated film can be applied to one surface or both surfaces of the glass plate.

As the transparent glass substrate in the present invention, a transparent glass article having a refractive index of 1.47 to 1.53, such as a non-colored glass plate having a transparent soda lime silicate glass composition, colored with green, bronze, or the like, or blocking ultraviolet rays or heat rays The glass plate which has the performance to make it, and the transparent glass substrate etc. which have other shapes may be used, The glass plate for PDP and other displays, the glass plate for automobiles, and the building glass plate of thickness 0.5-5.0 mm are used preferably, The glass plate The above antireflection film can be coated on one surface or both surfaces of the substrate. In the case where both surfaces of the plate-shaped antireflective coating glass article are used in contact with atmospheric or reduced pressure air or other gas, the visible light reflectance is best obtained by coating the antireflection coating or the antireflection coloring film on both surfaces of the glass substrate. You can do less. When one surface of the plate-shaped antireflection film-coated glass article is used, for example, bonded or adhered to various panels via a plastic film, the antireflection film is often sufficient only to cover the other surface of the above-described glass article.

The low-reflective glass article in which the anti-reflective film of the present invention is colored, in particular, a colored film-coated low-reflective glass plate used for a front glass, a car window, a building window, etc. of a display device such as a PDP, is preferably a Lab color system. In this case, a has a chromaticity in the range of -15.0 to 20.0, b in the range of -15.0 to 3.0, and L has a transmission color of 40 to 90. More preferably, it has a transmissive color represented by a Lab color system, where a is -5.0 to 10.0, b is a chromaticity in the range of -5.0 to 6.0, and L is at a brightness of 60 to 90.

The low reflection glass article which coat | covered the colored antireflective film of this invention provides the glass article which is excellent in the reflection reduction property, and provides the glass article which is excellent in designability by a coloring absorption film. Moreover, it can be used as an optical filter used in close contact with the front surface of a PDP in combination with the anti-reflective coloring film coating glass article of this invention, an electromagnetic wave shielding film, etc. In that case, since the selective absorption film is used, the optical filter which adjusts the light emission color of a PDP is provided. For example, in a PDP, since a blue-emitting phosphor has a property of slightly developing a red component in addition to blue, when a portion that should appear blue is displayed in a purple color, the red component of the phosphor is absorbed into the colored film of the present invention. In this way, the color emitted from the PDP can be balanced. In the case where a silver multilayer film is used as the electromagnetic wave shielding layer, the transmission color of the conventional filter becomes yellowish green, but the transmission color is used as the whole filter by using a thing in which the transmission color becomes purple as the anti-reflection coloring film of the present invention. It can be adjusted to neutral gray or blue gray.

The optical filter for plasma display panel which provided the electromagnetic wave shielding layer in the surface on the opposite side to the surface which coat | covered said anti-reflective coloring film is shown by the Lab table color system, where a is -3.0-3.0 and b is -3.0-3.0 It is preferable to have a transmissive color represented by. In addition to using a multilayered silver film as the electromagnetic wave shielding layer, a method in which an electroless plated of copper or copper nickel, which is a high-conductivity metal, to a mesh fabric made of synthetic resin is stretched and pasted onto a transparent substrate, and a low-resistance ITO film , A method of directly laminating a silver thin film, a multilayer film of a silver thin film on a transparent substrate, or a method of stretching the laminated film thereof onto a transparent substrate and the like.

Although the PDP has a front glass plate and a back glass plate as its components, the antireflection film-coated glass article of the present invention using a high distortion glass plate, that is, a glass substrate having a distortion point of 570 ° C or higher, as a transparent glass substrate is used as the front surface of the PDP. By using as a glass plate, the optical filter for PDPs and the front glass plate of a PDP can be used together, and the PDP which has an anti-reflective film on the surface can be provided.

Claims (17)

On a transparent glass substrate having a refractive index of 1.47 to 1.53, the first layer having a median refractive index (n ₁ ) of 1.60 to 1.95 and a film thickness of (60 to 130 nm) / n ₁ , and in the range of 1.91 to 2.60 And a second layer having a high refractive index (n ₂ ) and a film thickness of (140 to 230 nm) / n ₂ of at least 0.20 greater than the refractive index of the first layer described above, and within the range of 1.35 to 1.59. A low reflection glass in which three layers are laminated in this order with a third layer having a low refractive index (n ₃ ) and a film thickness of (110 to 150 nm) / n ₃ having a value of at least 0.20 smaller than that of the first layer. The article, wherein the second layer contains at least 70 mol% or more in total of at least one metal oxide selected from the group consisting of titanium oxide, cerium oxide, bismuth oxide, zirconium oxide, niobium oxide and decarburized oxide. Three layers contain 50-100 mol% of silicon oxide, and the said metal A total amount of cargo, and containing 0-10% by mole, the low reflection glass article of the above-described first layer is a metal oxide containing silicon oxide 15~80 mol%, and also the one characterized in that it contains 20 to 70% by mole in total. The method of claim 1, wherein 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 coefficient of 50 or more. Having a low reflection glass article. The low reflection glass article according to claim 1 or 2, wherein the first layer, the second layer and the third layer each have refractive indices n ₁ , n ₂ and n ₃ satisfying the following formula (2). 0.95 × n ₂ × n ₃ ≤n ₁ ² ≤1.10 × n ₂ × n ₃ (2) The said metal oxide contained in said 3rd layer is the same as said metal oxide contained in said 2nd layer, and is contained in said 1st layer in any one of Claims 1-3. A low reflection glass article, wherein the metal oxide is the same as the metal oxide described above contained in the second layer. The fine particles of the metal according to any one of claims 1 to 4, wherein at least one of the first to third layers is made of at least one metal selected from the group consisting of Group IB and Group VIII of the periodic table. A low reflection glass article containing 20 mol%. The said 1st layer contains 15-80 mol% silicon oxide and 20-70 mol% titanium oxide, The said 2nd layer is 0-30 mol%. Silicon oxide and 70 to 100 mol% titanium oxide, the third layer containing 85 to 100 mol% silicon oxide, at least one of the first layer, second layer and third layer The low reflection glass article containing these 0.5-20 mol% gold fine particles. According to claim 1 to 4, wherein any one of, the above-described first layer is titanium oxide, bismuth oxide and silicon oxide, TiO ₂ -Bi ₂ O ₃ -SiO each of TiO ₂ in the _second type ternary composition, Bi ₂ O _3, that the molar ratio of SiO ₂ coordinates (TiO _2, Bi ₂ O _3, SiO ₂ for each mole%) and represented by, M (30.5, 0.5, 69 ), N (68, 1, 31), O (3.5 , 65.5, 31) and P (1.5, 29.5, 69) at a ratio within the range of the square MNOP, wherein the second layer similarly denotes titanium oxide, bismuth oxide and silicon oxide by the above coordinate points , A (69, 1, 30), B (99, 1, 0), C (5, 95, 0) and D (3, 67, 30) at a ratio within the range of the rectangle ABCD, The third layer similarly denotes titanium oxide, bismuth oxide and silicon oxide at the coordinate points described above, such that Y (0, 0, 100), Z (29.5, 0.5, 70) and A '(1.5, 28.5, 70). Is a ratio within the range of the triangle YZA ' Low reflection glass article. The low reflection glass article according to any one of claims 1 to 7, wherein the transparent glass substrate is a glass plate having a thickness of 0.5 to 5.0 mm. The low reflection glass article according to claim 8, wherein the glass article is represented by a Lab color system, and a has a transmission color in which a is represented by a chromaticity of -15.0 to 20.0 and b is -15.0 to 3.0. The low reflection glass article according to claim 9, wherein the glass article is represented by a Lab color system, and a has a transmission color in which a is represented by a chromaticity of -10.0 to 10.0 and b is -12.0 to 0.0. The double-sided surface as claimed in claim 1, wherein the glass article comprises 5.0% or less visible light reflectance (reflection of the film surface and reflection on the back surface with respect to light incident from the film surface side at an incident angle of 12 degrees). Low light reflecting glass article). The low reflection glass article according to any one of claims 1 to 11, wherein the transparent glass substrate is a transparent glass plate having a high distortion point. An electromagnetic wave shielding layer is provided on the surface opposite to the surface on which the antireflective colored film is coated of the low reflection glass article according to any one of claims 8, 9, 10, and 12. Optical filter for panels. The optical filter for plasma display panel according to claim 13, wherein the optical filter described above has a transmission color represented by a Lab color system, where a is represented by a chromaticity of -3.0 to 3.0, and b is -3.0 to 3.0. A plasma display panel comprising the low reflection glass article according to any one of claims 8, 9, 10 or 12 as front glass. Applying the antireflection film-forming liquid composition formed by dissolving a metal compound capable of hydrolysis and condensation in an organic solvent to the surface of the transparent glass substrate, and then irradiating ultraviolet rays to the application surface described above, and to the applied substrate surface The manufacturing method of the low reflection glass article in any one of Claims 1-12 including the process of repeating the said application | coating process and said ultraviolet irradiation process twice. 17. The compound according to claim 16, wherein the metal compound is selected from titanium alkoxides, titanium halides or chelates thereof as titanium raw materials, bismuth nitrate as bismuth raw material, bismuth oxyacetic acid, bismuth chloride and bismuth alkoxides. At least one of a compound selected from cerium nitrate as a cerium raw material, a compound selected from cerium chloride, a silicon alkoxide as the silica raw material, an oligomer thereof, or a hydrolytic condensate thereof, and a gold compound as a gold particulate material or a gold colloid dispersion solution A method for producing a low light reflective glass article.