JP2000021336A - Glass article having conductive reflection preventive film and cathode-ray tube using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent electric resistance and visible radiation transmissivity from being largely changed even if heat treatment is received in a manufacturing process by forming a metallic film containing nickel by a specific quantity on a glass substrate, and setting visible radiation reflectivity not more than a specific value. SOLUTION: A metallic film 4 having a thickness of 1.5 to 8 mm is formed on a glass substrate 1 having a refractive index of 1.4 to 1.7 in a wave length of 550 nm by an iron alloy having the nickel content of 5 to 95 wt.%, and a high refractive index transparent dielectric film 5 having a refractive index of 2 to 2.4 in a wave length of 550 nm and a low refractive index transparent dielectric film 6 having a refractive index of 1.35 to 1.46 are formed in order for covering. Thus, the metallic film 4 restrains an electric resistance value from remarkably increasing by heating when a thermal property in a single component changes, and a thickness is set to 1.5 to 8 nm from a balance between an increase in the electric resistance value and transmissivity. A film thickness of the transparent dielectric films 5, 6 is also respectively set to 5 to 140 nm and 50 to 120 nm to prevent a color tone of reflection from becoming a conspicuous color.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass article coated with an antireflection film having both conductivity and light absorption. In particular, an electron beam accelerated like a cathode ray tube excites a phosphor and is used for a display device that displays an image by applying an adhesive such as a resin or a glass frit to a front surface of a display portion of the face plate. The present invention relates to a glass article such as a glass plate used and a cathode ray tube using the same.

[0002]

2. Description of the Related Art In a display device using a cathode ray tube, such as a television, a display quality is improved by reducing the reflectance of external light on a display surface. Further, in a display device using this cathode ray tube, since a high voltage is used by using an electron gun, the image display surface is charged, thereby attracting dirt and dust in the air. In order to prevent or suppress such a phenomenon caused by charging, the front surface of an image display device is made conductive.

It is said that when an electromagnetic wave is generated by an electron beam accelerated by a high voltage, this may adversely affect a human body. Therefore, the front surface of the display unit is covered with a conductive film for the purpose of shielding electromagnetic waves.

For the above-mentioned purpose, a glass plate coated with a conductive anti-reflection film is attached to a face plate of a cathode ray tube, or the outer surface of the face plate is directly coated with a conductive anti-reflection film. I have.

As a conductive anti-reflection film coated on a glass article for the purpose of improving the display quality of the above-mentioned cathode ray tube, there is disclosed a glass plate / metal / titanium oxide / titanium oxide disclosed in JP-A-64-70701. A laminate represented by silicon oxide, a laminate represented by glass plate / magnesium fluoride / metal / titanium oxide / magnesium fluoride disclosed in JP-A-1-180333, and Patent Publication 256
No. 5538 discloses a laminated body represented by glass / praseodymium titanate / metal / praseodymium titanate / magnesium fluoride.

It is disclosed that the metal film used in these prior arts is formed of a thin film of stainless steel, titanium, chromium, zirconium, molybdenum, nickel, and chromium.

[0007]

However, a metal or alloy specifically disclosed in the above prior art is used as a metal film, and a transparent dielectric film is laminated on the metal or alloy to form a conductive antireflection film. When the thickness of the metal film is set to 5 nm or less in order to increase the transmittance of visible light, there is a problem that the electric resistance is significantly increased and the antistatic function and the electromagnetic wave shielding function are significantly reduced.

Further, a cathode ray for heating and joining the face plate and the funnel with a glass frit after coating the front face of a glass face plate with an antireflection film using a metal or alloy disclosed in the above-mentioned prior art as a metal film. When the tube manufacturing method is adopted, the electric resistance of the conductive anti-reflection film is significantly increased in the heating step, and the transmittance is increased, so that the light absorbing property is secured and the excellent antistatic function is provided. It has been difficult to manufacture a cathode ray tube having the same. That is, in the prior art, it was not possible to solve the problem that the electrical resistance and the visible light transmittance of the conductive anti-reflection film did not change significantly even when the cathode ray tube was subjected to a heat treatment in the assembling process.

[0009]

SUMMARY OF THE INVENTION The first aspect of the present invention is to provide a 550
On a glass substrate having a refractive index of 1.4 to 1.7 at a wavelength of nm, a first layer metal film and a second layer
A high-refractive-index transparent dielectric film having a refractive index at a wavelength of 550 nm of the layer of 2.0 to 2.4, and a low-refractive index of a third layer having a refractive index at a wavelength of 550 nm of 1.35 to 1.46. A glass article coated with a conductive anti-reflection film on which a transparent dielectric film is laminated, wherein the metal film is a nickel-iron alloy film and has a visible light reflectance of 1% or less. Glass article with a conductive anti-reflection film.

The first metal film of the present invention needs to be an alloy film of nickel and iron. The nickel content in the metal film is preferably at least 5% by weight, more preferably at least 10% by weight. Most preferably, it is 70% by weight. If the nickel content is less than 5%, the metal film approaches the thermal properties of the metal film consisting of a single component of iron, and when heated, the electrical resistance value increases significantly and the transmittance greatly changes. It is not preferable.

Further, it is preferable that the nickel content in the metal film is 95% by weight or less. If the nickel content exceeds 95% by weight, the metal film approaches the thermal properties of a metal film consisting of a single component of nickel, and especially the metal film has a thickness of 4n.
When it is less than m, the electric resistance value is undesirably increased.

In the first aspect of the present invention, the thickness of the metal film is preferably set to 1.5 nm to 8 nm. 1.5 thickness
When the thickness is less than nm, the electric resistance value is undesirably increased. On the other hand, if the thickness exceeds 8 nm, the transmittance is reduced, and the displayed image is dark, which is not preferable.

Further, in the first aspect of the present invention, from the viewpoint of reducing the visible light reflectance to 1% or less and preventing the color tone of reflection from becoming conspicuous as a glass product used for a cathode ray tube, It is preferable that the thickness of the high refractive index transparent dielectric film is 5 nm to 140 nm, and the thickness of the low refractive index transparent dielectric film of the third layer is 50 nm to 120 nm.

A second aspect of the present invention is that, on a glass substrate having a refractive index of 1.4 to 1.7 at a wavelength of 550 nm, a metal film of a first layer and a metal film of a second layer are arranged in this order from the glass substrate side. A high-refractive-index transparent dielectric film having a refractive index of 2.0 to 2.4 at a wavelength of 550 nm, and a refractive index of the third layer at a wavelength of 550 nm of 1.7 to 1.7.
1.9 medium refractive index transparent dielectric film and fourth layer 550 nm
A glass article coated with an antireflection film having a low-refractive-index transparent dielectric film having a refractive index of 1.35 to 1.46 at a wavelength of, wherein the metal film is a nickel-iron alloy film; A glass article with a conductive antireflection film, wherein the visible light reflectance is 1% or less.

The second metal film of the present invention needs to be an alloy film of nickel and iron. The nickel content in the metal film is preferably at least 5% by weight, more preferably at least 10% by weight, and most preferably at least 70% by weight. If the nickel content is less than 5% by weight, the metal film approaches the thermal properties of the metal film consisting of a single component of iron, and when heated, the electrical resistance value increases significantly and the transmittance greatly changes. Is not preferred.

The nickel content in the metal film is preferably not more than 95% by weight. When the nickel content exceeds 95% by weight, the metal film approaches the thermal properties of the metal film composed of a single component of nickel, and particularly, the metal film has a thickness of 4n.
When it is less than m, the electric resistance value is undesirably increased.

In the second aspect of the present invention, it is preferable that the thickness of the metal film is 1.5 nm to 8 nm. When the thickness is 1.5 nm or less, the electric resistance remarkably increases, which is not preferable. On the other hand, if the thickness exceeds 8 nm, the transmittance is remarkably reduced, and the displayed image becomes dark.

Further, in the second aspect of the present invention, from the viewpoint of reducing the visible light reflectance to 1% or less and preventing the reflection color tone from becoming a noticeable color as a glass product used for a cathode ray tube, The thickness of the high refractive index transparent dielectric film is 5 nm to 70 nm, the thickness of the third layer medium refractive index transparent dielectric film is 10 nm to 100 nm, and the thickness of the fourth layer low refractive index transparent dielectric film is 50 nm to 50 nm. It is preferably 120 nm.

A third aspect of the present invention is that, on a glass substrate having a refractive index of 1.4 to 1.7 at a wavelength of 550 nm, a metal film of a first layer and a metal film of a second layer are arranged in this order from the glass substrate side. A high-refractive-index transparent dielectric film having a refractive index of 2.0 to 2.4 at a wavelength of 550 nm, a third metal film, and a fourth layer having a refractive index of 2.0 to 2 at a wavelength of 550 nm; .4 a high refractive index transparent dielectric film;
The refractive index of the fifth layer at a wavelength of 550 nm is 1.35-1.
46. A glass article coated with a conductive anti-reflection film having a low refractive index transparent dielectric film laminated thereon, wherein at least one of the first layer metal film and the third layer metal film is formed of a nickel-iron alloy. And a visible light reflectance of 1% or less.

Also in the third aspect of the present invention, the metal film needs to be an alloy film of nickel and iron. The nickel content in the metal film is preferably 5% by weight or more.
The content is more preferably 0% by weight or more, and most preferably 70% by weight or more. Nickel content is 5% by weight
If it is less than 1, the metal film approaches the thermal properties of the metal film composed of a single component of iron, and when heated, the electrical resistance value increases significantly, and the transmittance changes undesirably.

The nickel content in the metal film is preferably not more than 95% by weight. If the nickel content exceeds 95% by weight, the metal film approaches the thermal properties of the metal film composed of a single component of nickel, and particularly when the thickness is less than 4 nm, the electric resistance value is undesirably increased, which is not preferable.

In the third aspect of the present invention, the thickness of each of the first and third metal films is preferably 1.5 to 7.5 nm, and the total thickness is preferably 9 nm or less. The reason for limiting the respective thickness ranges of the metal layers is as follows.
Or it is the same as the second. If the total thickness exceeds 9 nm, it is not preferable because the antireflection film provided on the front surface of the display device has low transparency and the display screen is dark.

In the third aspect of the present invention, the second layer is formed from the viewpoint of reducing the visible light reflectance to 1% or less and preventing the color tone of reflection from becoming a conspicuous color as a glass product used for a cathode ray tube. The thickness of the high refractive index transparent dielectric film is 10 nm to 70 nm, the thickness of the high refractive index transparent dielectric film of the fourth layer is 10 nm to 70 nm, and the thickness of the low refractive index transparent dielectric film of the fifth layer is 70 nm to 120 nm. It is preferred that

In any of the first, second and third aspects of the present invention, a glass face plate or a transparent or colored glass plate can be used as the glass substrate, and the glass composition thereof is not particularly limited. Absent. For example, a glass having a soda-lime-silica composition, a borosilicate composition, an alumino-silicate composition, an alumino-borosilicate composition, or the like, which is processed by bending or air-cooling as necessary can be used.

In any of the first, second and third aspects of the present invention, praseodymium titanate (PrTiO ₃ ), titanium oxide (TiO ₂ ), and tantalum oxide (Ta ₂ O ₅ ) are used as the high refractive index transparent dielectric film. And zirconium oxide (Zr
O ₂ ) can be exemplified. Above all, praseodymium titanate is preferable because a transparent and dense film can be obtained without introducing oxygen gas when forming a film by vacuum deposition, and thus the metal film is not oxidized and deteriorated during the film formation.

In the first, second and third aspects of the present invention, examples of the low refractive index transparent dielectric film include magnesium fluoride and silicon dioxide. Among them, magnesium fluoride is preferable because the refractive index is as low as 1.35 and the difference from the refractive index of the high-refractive-index transparent dielectric film is large, so that it is easy to lower the reflectance.

In the second embodiment of the present invention, examples of the medium-refractive-index transparent dielectric film include magnesium oxide (MgO), niobium oxide (Nb ₂ O ₅ ), and silicon monoxide (SiO). Among them, magnesium oxide is preferable because a transparent and dense film can be obtained without introducing oxygen gas at the time of film formation by vacuum deposition, so that the metal film is not oxidized and deteriorated during the film formation.

In the first, second, and third aspects of the present invention, a transparent dielectric layer (hereinafter, referred to as a base film) may be provided between the glass substrate and the first layer metal film. This underlayer film cuts off the contact between the glass surface and the first layer metal film, that is, prevents impurities such as moisture on the glass surface from entering the metal film and prevents the electric resistance of the metal film from increasing. It is provided for the purpose of doing.

The material constituting the base film is not particularly limited, but praseodymium titanate, magnesium oxide, and magnesium fluoride (MgF ₂ ) can be exemplified as preferable ones.

The thickness of the underlayer is preferably 3 nm or more from the viewpoint of smoothing the metal film of the first layer and thereby reducing the electric resistance of the metal film. The thickness is preferably 7 nm or less, more preferably 5 nm or less, from the viewpoint of reducing the surface irregularities of the base film itself.

In any of the first, second and third embodiments of the present invention, the metal layer made of nickel and iron has the above-mentioned heat resistance in order to finely adjust the degree of light absorption and the reflection color tone. The third metal may be added as long as the third metal does not significantly deteriorate.

Each layer constituting the first, second and third conductive antireflection films of the present invention can be formed by a known method such as a vacuum evaporation method and an ion plating method.

The cathode ray tube according to the present invention is also provided with a conductive anti-reflection film according to the present invention after the face plate and the funnel are joined by a method of heating and joining the face plate and the funnel coated with the conductive anti-reflection film according to the present invention. It can also be produced by a method of coating a film.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings and embodiments. FIG. 1 is a cross-sectional view of an embodiment of an article 1 having a conductive anti-reflection film according to the present invention. An image display section of a glass face plate 3 is covered with a conductive anti-reflection film 2.

FIG. 2 is a partial cross-sectional view for explaining a laminated structure of the conductive anti-reflection film 2 of the present invention. FIG. 2 (a)
The conductive anti-reflection film 2 is configured such that a metal film 4, a high refractive index transparent dielectric film 5, and a low refractive index transparent dielectric film 6 are sequentially laminated on a face plate 3. FIG.
In (b), the conductive anti-reflection film 2 is such that a metal film 4, a high-refractive-index transparent dielectric film 5, a medium-refractive-index transparent dielectric film 7, and a low-refractive-index transparent dielectric film 6 are formed on a face plate 3. It is configured by being sequentially laminated. In FIG. 2C, the conductive anti-reflection film 2 is composed of a base film 8, a metal film 4, a high-refractive-index transparent dielectric film 5, a metal film 4, and a high-refractive-index transparent dielectric film 5 on a face plate 3. And the low-refractive-index transparent dielectric film 6 are sequentially laminated.

FIG. 3 is a graph showing the spectral characteristics of reflection and transmission in the visible light range of the sample obtained in Example 6 of the present invention.

In the following examples and comparative examples, the vapor deposition materials used when each film was formed by vacuum vapor deposition are as follows. -Nickel-iron film of Example: alloy wire of nickel and iron having a predetermined composition-Nickel film of Comparative Examples 1 and 3: Nickel wire-Iron film of Comparative Example 2: Iron wire-Nickel-iron chromium film of Comparative Examples 4 and 5 : Nickel-iron chrome alloy wire of predetermined composition-Nickel chromium film of Comparative Example 6: Nickel chromium alloy wire of predetermined composition-Praseodymium titanate film: Trade name S manufactured by Merck
UBSTANCEH2 pellet ・ Magnesium oxide film: Magnesium oxide particles ・ Magnesium fluoride film: Magnesium fluoride particles

Example 1 A well-washed 100 mm × 100 mm × thickness 3 mm glass plate of soda lime silica composition was placed in a vacuum evaporation tank.
300 by the substrate heater installed in the evaporation apparatus
In a state heated to ° C., a conductive antireflection film having a laminated structure shown in the column of Example 1 of Table 1 was coated on a glass plate. The evaporation material was evaporated by an electron beam evaporation method, the distance from the evaporation crucible to the glass plate was set to 100 cm, and the evaporation was performed while rotating the glass plate. The ultimate degree of vacuum before the start of vapor deposition was exhausted to 0.003 Pa with an oil diffusion pump for each film. The nickel-iron alloy film, praseodymium titanate film, magnesium fluoride film and magnesium oxide film were deposited without introducing oxygen gas.

The obtained sample was taken out of the vapor deposition apparatus, and the transmittance (wavelength: 550 nm), the reflectance on the film-coated side (wavelength: 550 nm), and the sheet resistance were measured as evaluation characteristics of antistatic performance. The composition of the metal film was measured by chemical analysis. Table 2 shows the measurement results. Further, the transmittance, the reflectance on the film-coated side, and the sheet resistance after heat-treating the sample at 450 ° C. for 1 hour in the atmosphere were measured. The results are shown in the column of Example 1 in Table 2.

[0040]

[Table 1] ==================================== Example membrane 1 2 3 4 5 6 7 8 9 10 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 1 NiFe NiFe NiFe PrTiO ₃ PrTiO ₃ NiFe MgO PrTiO ₃ PrTiO ₃ NiFe 3.2 3.2 3.2 5.0 5.0 4.6 5.0 5.0 5.0 3.2 2 PrTiO ₃ PrTiO ₃ PrTiO ₃ NiFe NiFe PrTiO ₃ NiFe NiFe NiFe PrTiO ₃ 127.4 127.4 127.4 2.0 3.2 26.0 4.6 2.2 2.4 34.8 3 MgO MgO MgO PrTiO ₃ PrTiO ₃ NiFe PrTiO ₃ PrTiO ₃ PrTiO ₃ MgF ₂ 45.4 45.4 45.4 101.4 134.5 2.4 26.0 34.8 34.8 93.6 4 MgF ₂ MgF ₂ MgF ₂ MgO MgF ₂ PrTiO ₃ NiFe MgF ₂ MgF ₂ 71.7 71.7 71.7 36.3 96.8 35.0 2.4 93.6 93.6 5 MgF ₂ MgF ₂ PrTiO ₃ 80.8 79.0 35.0 6 MgF ₂ 79.0 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Metal film composition Fe 20 10 30 20 50 20 40 95 5 5 Ni 80 90 70 80 50 80 60 5 95 95 ===================== =============== The upper part is the material of the film, the lower part is the thickness of the film (unit: nm), and the composition of the metal film is% by weight.

The reflectivity of the sample was 1% or less, which is required from a practical point of view, and this value was maintained at 1% or less without being significantly changed even after the heat treatment. Also, the sheet resistance is 2
The resistance was 82 Ω / □, which is low enough to have an antistatic function, and the resistance did not deteriorate (increased), but rather decreased, even when subjected to heat treatment. In addition, the transmittance was a small change of only 1.7% from 66.5% to 67.2%. This value was a front glass panel to be attached to the face plate of a cathode ray tube or a transparent face plate, and the useful transmittance from a practical viewpoint was in the range of 40 to 80%.

[0042]

[Table 2] ================================= Transmittance (%) Reflectivity (%) Sheet Resistance (Ω / □) Example Before and after Difference Before and after Difference Before and after Difference --------------- Example 1 66.5 67.2 0.7 0.22 0.25 0.03 282 258 -24 Example 2 65.2 66.3 1.1 0.26 0.28 0.02 305 245 -60 Example 3 66.0 67.8 1.8 0.23 0.29 0.06 295 226 -69 Example 4 75.2 76.2 1.0 0.25 0.26 0.01 207 174- 33 Example 5 67.0 67.7 0.7 0.19 0.30 0.11 198 184 -14 Example 6 47.0 49.2 2.2 0.11 0.28 0.17 98 96 -2 Example 7 46.6 47.5 0.9 0.17 0.20 0.03 87 85 -2 Example 8 61.2 61.8 0.6 0.81 0.85 0.04 341 330 -11 Example 9 70.2 70.2 0.0 0.70 0.50 0.20 279 247 -32 Example 10 67.2 67.6 0.4 0.34 0.41 0.07 486 484 -2 ===================== ============= Before: Before heat treatment, After: Heat treatment Difference after heat treatment - before heat treatment value

Examples 2 to 10 In the same manner as in Example 1, a conductive antireflection film having a film constitution shown in Table 1 was coated on a glass plate. Table 2 shows the results of the same test. In each of the samples of Examples 2 to 10, the reflectance was 1% or less both at the initial stage and after the heat treatment. The initial sheet resistance of each sample was 500Ω /
□ It was found to be as low as below, and that it did not increase significantly even after heat treatment, but rather decreased. The change in transmittance due to the heat treatment was a small value of 2.2% or less.

[0044]

Table 3 ================================ Comparative Example Film 1 2 3 4 5 6 ---- −−−−−−−−−−−−−−−−−−−−−−−−−−−−− 1 NiFe PrTiO ₃ NiFeCr NiFeCr NiCr 3.2 3.2 5.0 3.2 4.6 3.2 2 PrTiO ₃ PrTiO ₃ Ni PrTiO ₃ PrTiO ₃ PrTiO ₃ 127.4 127.4 3.2 127.4 26.0 127.4 3 MgO MgO PrTiO ₃ MgO NiFeCr MgO 45.4 45.4 134.5 45.4 2.4 45.4 4 MgF ₂ MgF ₂ MgF ₂ MgF ₂ PrTiO ₃ MgF ₂ 71.7 71.7 96.8 71.7 35.0 71.7 5 MgF ₂ 79.0 −− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Metal film Ni Fe Ni Ni: Fe: Cr Ni: Fe: Cr Ni: Cr Composition 100 100 100 60:12:28 76: 9: 16 80:20 ================================= Upper row Is the material of the film, the bottom is the thickness of the film (unit: nm), and the composition of the metal film is wt%

The fourth embodiment is obtained by adding a base film of praseodymium titanate to the film configuration of the second embodiment.
Example 7 is a film obtained by adding a praseodymium titanate underlayer to the film configuration of Example 7. Comparing Example 2 with Example 4, and Example 6 with Example 7, it can be seen that the sheet resistance is reduced by additionally inserting the underlayer.

Comparative Example 1 A comparative sample in which the metal film was a film of a single nickel composition and the conductive antireflection film having a laminated structure shown in the column of Comparative Example 1 in Table 3 was coated in the same manner as in Example 1 was used. Obtained. The results of evaluating this comparative sample in the same manner as in Example 1 are shown in the column of Comparative Example 1 in Table 4. This comparative sample has a reflectance of 1
% Or less, and the thermal stability of the transmittance was good, but the initial sheet resistance and after the heat treatment were 2M (mega) Ω / □ or more, and a good antistatic function could not be obtained. .

[0047]

[Table 4] ================================= Transmittance (%) Reflectivity (%) Sheet Resistance (Ω / □) Example Before and after Difference Before and after Difference Before and after Difference --------------- Example 1 62.6 63.1 0.5 0.45 0.58 0.13> 2M> 2M Comparative Example 2 64.3 83.0 18.7 0.43 4.20 4.08> 2M> 2M Comparative Example 3 63.6 64.2 0.6 0.65 0.52 -0.13> 2M> 2M Comparative Example 4 66.7 76.5 9.8 0.37 1.54 1.17 1140 2950 1810 Comparative Example 5 47.3 56.5 9.2 0.25 0.34 0.09 1173 554 -619 Comparative Example 6 63.2 75.7 12.5 0.51 3.10 2.59 769 406K ======================== ========= Before: Before heat treatment, After: After heat treatment Difference is after heat treatment-Before heat treatment

Comparative Example 2 A comparative sample in which the metal film was a film of a single iron composition and a conductive antireflection film having a laminated structure shown in the column of Comparative Example 2 in Table 3 was coated in the same manner as in Example 1 was used. Obtained. The results of evaluating this comparative sample in the same manner as in Example 1 are shown in the column of Comparative Example 2 in Table 4. The initial reflectance of this comparative sample is 0.
Although the value was as low as 43%, the transmittance was 1 due to the heat treatment.
The reflectance rose to 8.7%, and the reflectance rose to 4.08%.
The sheet resistance was 2 M (mega) Ω or more both at the initial stage and after the heat treatment, and a good antistatic function could not be obtained.

Comparative Example 3 A laminate in which the metal film was a film of a single composition of nickel, and a base film of praseodymium titanate was provided between the glass plate and the first metal layer as shown in the column of Comparative Example 3 in Table 3. A comparative sample of the configuration was obtained. The results of evaluating this comparative sample in the same manner as in Example 1 are shown in the column of Comparative Example 3 in Table 4. The reflectance before and after the heat treatment was 1% or less, and the thermal stability of the transmittance was good.
M (mega) Ω / □ or more, and a good antistatic function could not be obtained.

Comparative Examples 4 and 5 The metal film was a three-component film of nickel, iron and chromium.
Comparative samples having a laminated configuration shown in the columns of Comparative Example 4 and Comparative Example 5 in Table 3 were obtained. The results of evaluating this comparative sample by the same method as in Example 1 are shown in the columns of Comparative Example 4 and Comparative Example 5 in Table 4. The comparative sample containing 28% by weight of chromium
It was found that the change in transmittance due to the heat treatment increased by 9.8%, and that of Comparative Sample 5, which contained 16% of chromium, increased by 9.2%, and the thermal stability was significantly deteriorated. In addition, it was recognized that the heat resistance caused an irregular change in the sheet resistance, which increased in Comparative Sample 4 and decreased in Comparative Sample 5.

Comparative Example 6 A comparative sample was obtained in the same manner as in Comparative Example 1 except that the metal film was a two-component system of nickel and chromium. Table 4
As shown in the column of Comparative Example 6, the change in the transmittance of the comparative sample due to the heat treatment was as large as 12.5%, and the sheet resistance was increased by three orders of magnitude.

As described above, none of the comparative samples had characteristics in which both the transmittance and the sheet resistance were stable with respect to the heat treatment. In contrast,
In the sample of the example of the present invention, it can be seen that the transmittance and the reflectance are stable even after the heat treatment, the sheet resistance is rather reduced, and both the antistatic function and the electromagnetic wave shielding function are maintained.

In a display device such as a cathode ray tube for displaying a phosphor by irradiating the phosphor with an electron beam at an accelerated rate, the conductive performance of the conductive antireflection film having an antistatic function provided on the front surface of the image display section is approximately equal to the sheet resistance. It is preferably 1 kΩ / □ or less, and is preferably about 500 Ω / □ or less in order to have the ability to block emitted electromagnetic waves in consideration of the effect on the human body. From this viewpoint, it can be seen that the conductive anti-reflection film of the sample obtained in the example of the present invention has sufficient practical performance.

As described above, according to the present invention, the metal film of the antireflection film made of a laminate of the metal film and the transparent dielectric film is
When composed of a single film of nickel or a single film of iron,
The electrical resistance deteriorates (increases) when they are subjected to a heat treatment, but surprisingly, the unexpected effect of improving the stability of the electrical resistance by forming an alloy film of nickel and iron has been found through experiments. It was done.

[0055]

According to the present invention, since the metal film constituting the conductive anti-reflection film of the present invention is made of an alloy film of nickel and iron, the conductive anti-reflection film has excellent thermal stability. Therefore, even if it is subjected to a high-temperature heat treatment, its transmittance and reflectance change little. Further, since the metal film of the conductive anti-reflection film is formed of a film of an alloy of nickel and iron, its sheet resistance is stable even when subjected to a high-temperature heat treatment.

Since the optical characteristics and the electrical resistance characteristics of the conductive anti-reflection film of the present invention are thermally stable, the glass face plate coated with the conductive anti-reflection film of the present invention is heated with a funnel and frit glass. Even before the bonding, the performance before the heat bonding can be maintained, and the cathode ray tube can be manufactured without impairing the optical characteristics and the antistatic function.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of one embodiment of an article with a conductive anti-reflection film of the present invention.

FIG. 2 is a partial cross-sectional view for explaining a laminated structure of a conductive antireflection film of the present invention.

FIG. 3 is a diagram showing transmission and reflection characteristics in a visible region according to the embodiment of the present invention.

[Explanation of symbols]

 1: Glass article with conductive antireflection film 2: Conductive antireflection film 3: Glass substrate 4: Metal film 5: High refractive index transparent dielectric film 6: Low refractive index transparent dielectric film 7: Medium refractive index transparent dielectric Body film 8: Base film

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Koji Nakanishi 3-5-11, Doshomachi, Chuo-ku, Osaka-shi, Osaka Inside Nippon Sheet Glass Co., Ltd. (72) Etsuo Ogino 3 Doshomachi, Chuo-ku, Osaka-shi, Osaka 5-11 No.5 Nippon Sheet Glass Co., Ltd. F-term (reference) 5C032 AA02 DD02 DE01 DE03 DF05 DG01 DG02

Claims (15)

[Claims] 1. The refractive index at a wavelength of 550 nm is 1.4 to
A first layer of a metal film and a second layer of a high-refractive-index transparent dielectric material having a refractive index at a wavelength of 550 nm of 2.0 to 2.4 on a glass substrate of 1.7 in order from the glass substrate side. A glass article coated with a film and a conductive antireflection film in which a low-refractive-index transparent dielectric film having a refractive index of 1.35 to 1.46 at a wavelength of 550 nm of a third layer is laminated. A glass article with a conductive antireflection film, wherein the metal film is a nickel-iron alloy film and the visible light reflectance is 1% or less. 2. The method according to claim 1, wherein the nickel content in the metal film is 5% by weight.
The glass article with a conductive anti-reflection film according to claim 1, wherein the glass article is not less than 95% by weight. 3. The glass article with a conductive antireflection film according to claim 1, wherein the thickness of the metal film is 1.5 nm to 8 nm. 4. The high refractive index transparent dielectric film of the second layer has a thickness of 5 nm to 140 nm, and the low refractive index transparent dielectric film of the third layer has a thickness of 50 nm to 120 nm. A glass article with a conductive anti-reflection film according to the above item. 5. The refractive index at a wavelength of 550 nm is 1.4 to
A first layer of a metal film and a second layer of a high-refractive-index transparent dielectric material having a refractive index at a wavelength of 550 nm of 2.0 to 2.4 on a glass substrate of 1.7 in order from the glass substrate side. The film, the middle-refractive-index transparent dielectric film having a refractive index at the wavelength of 550 nm of the third layer of 1.7 to 1.9, and the refractive index of the fourth layer at the wavelength of 550 nm of 1.35 to 1. 46. A glass article coated with a conductive anti-reflection film on which a low refractive index transparent dielectric film is laminated, wherein the metal film is a nickel-iron alloy film and the visible light reflectance is 1% or less. A glass article with a conductive antireflection film, characterized by the following. 6. The nickel content in the metal film is 5% by weight.
The glass article with a conductive anti-reflection film according to claim 5, wherein the glass article is not less than 95% by weight. 7. The glass article with a conductive anti-reflection film according to claim 5, wherein the thickness of the metal film is 1.5 nm to 8 nm. 8. The transparent dielectric film having a high refractive index of the second layer having a thickness of 5 nm to 70 nm, the transparent dielectric film having a middle refractive index of the third layer having a thickness of 10 nm to 100 nm, and the transparent dielectric film having a low refractive index of the fourth layer. The glass article with a conductive antireflection film according to any one of claims 5 to 7, wherein the thickness of the body film is 50 nm to 120 nm. 9. The refractive index at a wavelength of 550 nm is 1.4 to 9.
A first layer of a metal film and a second layer of a high-refractive-index transparent dielectric material having a refractive index at a wavelength of 550 nm of 2.0 to 2.4 on a glass substrate of 1.7 in order from the glass substrate side. The refractive index at a wavelength of 550 nm of the film, the metal film of the third layer, and the fourth layer is 2.
A high-refractive-index transparent dielectric film of 0 to 2.4;
A glass article coated with a conductive anti-reflection film having a low refractive index transparent dielectric film having a refractive index of 1.35 to 1.46 at a wavelength of nm. At least one of the three metal films is a nickel-iron alloy film,
A glass article with a conductive antireflection film, wherein the visible light reflectance is 1% or less. 10. The method according to claim 9, wherein the nickel content in the metal film is not less than 5% by weight and not more than 95% by weight.
The glass article with a conductive anti-reflection film according to the above. 11. The conductive film according to claim 9, wherein the first and third metal films have a thickness of 1.5 nm to 7.5 nm, respectively, and a total thickness thereof is 9 nm or less. Glass article with anti-reflective coating. 12. The high refractive index transparent dielectric film of the second layer has a thickness of 10 nm to 70 nm, the high refractive index transparent dielectric film of the fourth layer has a thickness of 10 nm to 70 nm, and the fifth layer has a low refractive index transparent dielectric film. The glass article with a conductive antireflection film according to any one of claims 9 to 11, wherein the thickness of the body film is 70 nm to 120 nm. 13. A transparent dielectric film is provided between the glass substrate and the first metal film.
The glass article with a conductive antireflection film according to any one of the above. 14. The glass article with a conductive antireflection film according to claim 1, wherein the glass substrate is a glass face plate for a cathode ray tube. 15. A cathode ray tube obtained by heating and joining the glass article with a conductive antireflection film according to claim 14 to a funnel with a glass frit.