WO2000002066A1

WO2000002066A1 - Glass product with conductive antireflection film and cathode ray tube using it

Info

Publication number: WO2000002066A1
Application number: PCT/JP1999/003494
Authority: WO
Inventors: Terufusa Kunisada; Yasunori Taninaka; Koji Nakanishi; Etsuo Ogino
Original assignee: Nippon Sheet Glass Company, Limited
Priority date: 1998-07-01
Filing date: 1999-06-29
Publication date: 2000-01-13
Also published as: KR20010071668A; ES2212863A1; CN1307688A; JP2000021336A; ES2212863B1; TW428202B

Abstract

A glass product covered with a conductive antireflection film comprising a glass substrate with a refractive index of 1.4 to 1.7 at a wavelength of 550 nm and, laminated on the glass substrate in the mentioned order from the substrate side, a metal film, a high-refractive-index, transparent dielectric film with a refractive index of 2.0 to 2.4 and a low-refractive-index, transparent dielectric film with a refractive index of 1.35 to 1.46, wherein the metal film is a nickel-iron alloy film and has a visible light reflection factor of 1 % or lower. A cathode ray tube capable of being produced with performances before heat bonding maintained and without sacrifice in optical characteristics and antistatic functions even when heat bonded with a funnel and fritted glass because the conductive antireflection film has thermally stabilized optical and electric resistance characteristics.

Description

Description Glass article with conductive anti-reflective coating and cathode ray tube using the same

The present invention relates to a glass article coated with an antireflection film having both conductivity and light absorption. In particular, a resin plate or glass frit etc. is used on the front of the display section of a faceplate used in a display device that displays an image by exciting a phosphor with an accelerated electron beam such as a cathode ray tube. The present invention relates to a glass article such as a glass plate used by bonding with an adhesive, and a cathode ray tube using the same. Background art

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 lowering a reflection rate 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 dust and dirt in the air. In order to prevent or suppress the phenomenon caused by such charging, the front surface of the image display device is made conductive.

In addition, it is said that if an electromagnetic wave is generated by an electron beam accelerated by a high voltage, this may have an adverse effect on the 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 an outer surface of a face plate is directly coated with a conductive anti-reflection film.

As the conductive anti-reflection film coated on the glass article for the purpose of improving the display quality of the above-mentioned cathode ray tube, the glass plate / metal Z oxide disclosed in JP-A-64-77001 can be used. A laminate represented by titanium / silicon oxide, or a glass plate / magnesium fluoride / metal / titanium oxide / fiber disclosed in Japanese Patent Application Laid-Open No. 1-180333 is disclosed. There is a laminate represented by magnesium fluoride and a laminate represented by glass plate / praseodymium thiocyanate / metal / praseodymium titanate / magnesium fluoride disclosed in Patent Publication No. 256553/38. .

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

However, a metal or alloy specifically disclosed in the above-mentioned prior art is used as a metal film, and a transparent dielectric film is laminated on the metal or alloy to form a conductive anti-reflection film, which increases the transmittance of visible light. Therefore, when the thickness of the metal film is reduced to 5 nm or less, there is a problem that the electric resistance is significantly increased and the antistatic function and the electromagnetic wave shielding function are significantly reduced.c. When a cathode ray tube manufacturing method is used, in which the anti-reflection film used for the metal film is coated on the front surface of the glass face plate and the face plate and the funnel are heated and joined with a glass frit, the conductive anti-reflection is used in the heating process Since the electrical resistance of the film increases significantly and the transmittance increases, a cathode ray tube that ensures light absorption and has an excellent antistatic function is manufactured. It was difficult to build. That is, the conventional technology could not solve the problem that the electrical resistance and the visible light transmittance of the conductive antireflection film did not change significantly even when the cathode ray tube was subjected to a heat treatment in the assembling process. Disclosure of the invention

A first 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 first layer metal film and a second layer A high-refractive-index transparent dielectric film having a refractive index of 2.0 to 2.4 at a wavelength of 55 O nm and a refractive index of 1.35 to 1.3 at a wavelength of 55 O nm of the third layer. 46 A glass article coated with a conductive anti-reflection film laminated with a low-refractive-index transparent dielectric film according to 6, wherein the metal film is a nickel-iron alloy film and has a visible light reflectance of 1% or less. A glass article provided with a conductive anti-reflection film. (Hereinafter, this is referred to as a first embodiment.)

A second aspect of the present invention is a glass substrate having a refractive index of 1.4 to 1.7 at a wavelength of 550 nm. A first layer of a metal film, a second layer of a high-refractive-index transparent dielectric film having a refractive index of 2.0 to 2.4 at a wavelength of 55 Onm, The refractive index of the layer at a wavelength of 55 Onm has a refractive index of 1.7 to 1.9, and the fourth layer has a refractive index of 1.35 to 1.46 at a wavelength of 55 Onm. A glass article coated with an anti-reflection film laminated with a low-refractive-index transparent dielectric film, wherein the metal film is a nickel-iron alloy film and has a visible light reflectance of 1% or less. This is a glass article with a conductive anti-reflection film. (Hereinafter, this is referred to as a second aspect.)

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 55 Onm, a metal film of a first layer and a 55 High refractive index transparent dielectric film with a refractive index of 2.0 to 2.4 at a wavelength of, a third layer of metal film, and a refractive index of a fourth layer at a wavelength of 55 Onm of 2.0 to 2 The conductive anti-reflective coating is composed of a high-refractive-index transparent dielectric film of No. 4 and a low-refractive-index transparent dielectric film of a fifth layer having a refractive index at a wavelength of 550 nm of 1.35 to 1.46. A coated glass article, characterized in that at least one of the first layer metal film and the third layer metal film is made of a nickel-iron alloy and has a visible light reflectance of 1% or less. It is a glass article with a conductive anti-reflection film. (Hereinafter referred to as a third embodiment.) Brief description of the drawings

FIG. 1 is a cross-sectional view of an embodiment of the article with a conductive antireflection film of the present invention. FIG. 2 is a partial cross-sectional view for explaining a laminated structure of the conductive anti-reflection film of the present invention. FIG. 3 is a diagram showing transmission and reflection characteristics in the visible region according to the embodiment of the present invention.

Numerical values in the figure are as follows: 1: Glass article with conductive anti-reflective coating, 2: Conductive anti-reflective coating, 3: Glass substrate, 4: Metal film, 5: High refractive index transparent dielectric film, 6: Low refractive index transparent dielectric film,: Medium refractive index transparent dielectric film, 8: Underlayer. BEST MODE FOR CARRYING OUT THE INVENTION

The metal film of the first embodiment of the present invention needs to be a nickel-iron alloy film. The nickel content in the metal film is preferably 5% by weight or more, More preferably, the amount is at least%. It is most preferable that the content be 70% by weight or more. If the nickel content is less than 5%, the metal film approaches the thermal properties of a metal film consisting of a single component of iron, and when heated, the electrical resistance increases significantly and the transmittance changes significantly. Is not preferred.

Further, the nickel content in the metal film is preferably 95% by weight or less. When the nickel content exceeds 95% by weight, the metal film approaches the thermal properties of a metal film composed of a single component of nickel, and the electrical resistance becomes remarkable especially when the thickness of the metal film is less than 4 nm. It is not preferable because it rises.

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

Further, in the first embodiment 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 a noticeable color as a glass product used for a cathode ray tube, the height of the second layer is increased. The thickness of the refractive index transparent dielectric film is 5ηπ! And the thickness of the low-refractive-index transparent dielectric film of the third layer is set to 5 ηπ! It is preferable to set to ~ 12 Onm.

The metal film according to the second aspect of the present invention needs to be a nickel-iron alloy film. The nickel content in the metal film is preferably at least 5% by weight, more preferably at least 10% by weight, 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 a metal film composed of a single component of iron, and when heated, the electrical resistance value increases significantly and the transmittance increases. It is not preferable because it changes.

Further, the nickel content in the metal film is preferably 95% by weight or less. When 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 the electrical resistance becomes remarkable especially when the thickness of the metal film is less than 4 nm. It is not preferable because it rises.

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

Further, in the second embodiment 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 noticeable as a glass product used for a cathode ray tube, the height of the second layer is increased. The thickness of the refractive index transparent dielectric film is 5ηπ! And the thickness of the third layer of the medium refractive index transparent dielectric film is 10 η π! 1100 nm, and the thickness of the fourth layer of the low refractive index transparent dielectric film is preferably 50 nm 1120 nm.

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 at least 5% by weight, more preferably at least 10% by weight, and most preferably at least 0% by weight. If the nickel content is less than 5% by weight, the metal film approaches the thermal properties of a metal film composed of a single component of iron, and when heated, the electrical resistance increases significantly and the transmittance increases. It is not preferable because it greatly changes.

Further, the nickel content in the metal film is preferably 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 the electrical resistance increases significantly, especially when the thickness is less than 4 nm. Is not preferred.

In a third embodiment of the present invention, the thickness of each of the first and third metal films is 1.5 ηπ! It is preferable that the total thickness be 9 nm or less. The reason for limiting the thickness range of each metal layer is the same as in the first or second embodiment of the present invention. If the total thickness exceeds 9 nm, the transparency becomes small as an antireflection film provided on the front surface of the display device, and the display screen becomes dark, which is not preferable.

Further, in the third embodiment 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, the height of the second layer is increased. When the thickness of the refractive index transparent dielectric film is 1 η η π! ~ 7 O nm, the thickness of the high refractive index transparent dielectric film of the fourth layer is 10 nm-70 nm, and the thickness of the low refractive index transparent dielectric film of the fifth layer is 70 nm ~ 120 nm. Is preferred. In any of the first, second, and third aspects of the present invention, a glass face plate or a transparent or colorless glass plate can be used as the glass substrate, and the glass composition thereof is particularly limited. is not. 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. The first aspect of the present invention, the second aspect, in any of the third aspect, titanate Puraseojiumu as a high refractive index transparent Yuden film _{(P r T i 0 3)} , titanium oxide (T i 0 _2), oxide tantalum (T a ₂ 0 ₅₎ and Sani匕zirconium (Z R_〇 ₂₎ film of Ru one 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 therefore, 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 between the refractive index and 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 aspect of the present invention, a medium refractive index transparent dielectric Ji as the trillions oxide Maguneshiumu (M g O), Ru can be exemplified niobium oxide (N b ₂ 0 ₅₎ and silicon monoxide (S I_〇) or the like. 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) can be provided between the glass substrate and the first layer metal film. This underlayer film breaks contact between the glass surface and the first metal film, that is, prevents water and other impurities on the glass surface from entering the metal film, thereby preventing the electrical 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 base film is preferably 3 nm or more from the viewpoint of smoothing the first metal film and thereby reducing the electrical resistance of the metal film. The thickness is preferably 7 nm or less, and 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 aspects of the present invention, the metal layer made of nickel and iron has the above heat resistance in order to finely adjust the degree of light absorption and the reflection color tone. A third metal may be added as long as the properties are not significantly deteriorated.

Each layer constituting the conductive anti-reflection film according to the first, second, and third aspects of the present invention can be formed by a known method such as a vacuum evaporation method or a ion plating method. The cathode ray tube is a ferrite coated with the conductive antireflection film according to the present invention.

Alternatively, it can be manufactured by a method of heating and joining a plate and a funnel, or by a method of joining a conductive antireflection film according to the present invention after joining a π-plate and a funnel.

The present invention will be described below with reference to the drawings and examples.

FIG. 1 is a cross-sectional view of an embodiment of an article 1 with a conductive anti-reflection film according to the present invention, in which a glass anti-reflection film 2 is coated with a conductive anti-reflection film 2 on an image display portion. Let's do it. FIG. 2 is a partial cross-sectional view for explaining a laminated structure of the conductive anti-reflection film 2 of the present invention. In FIG. 2 (a), the conductive anti-reflection film 2 is configured by sequentially laminating a metal film 4, a high-refractive-index transparent dielectric film 5, and a low-refractive-index transparent dielectric film 6 on a face plate 3. ing. In FIG. 2 (b), the conductive anti-reflection film 2 is composed of 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 The transparent dielectric films 6 are sequentially laminated. In FIG. 2 (c), 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 on a face plate 3. 5 and a low refractive index transparent dielectric film 6 are sequentially laminated.

FIG. 3 is a spectral characteristic diagram of reflection and transmission in the visible light region of the sample obtained in Example 6 of the present invention.

In the following Examples and Comparative Examples, each film was used when formed by vacuum evaporation. The deposited materials used are as follows.

Nickel-iron film of Example: Nickel-iron alloy wire of predetermined composition

Nickel film of Comparative Examples 1 and 3: Nickel wire

Iron film of Comparative Example 2: iron wire

Nickel-iron alloy films of Comparative Examples 4 and 5: Nickel-alloy alloy films of predetermined composition Nickel-chromium film of Comparative Example 6: Nickel-chromium alloy wires of specific composition Praseodymium titanate film: Me r ck brand name SUB STANCEH 2

· Magnesium oxide film: Magnesium oxide grains

Magnesium fluoride film: Magnesium fluoride particles Example 1

A well-washed 10 mm Ox100 mm x 3 mm thick glass plate of soda lime silica composition was placed in a vacuum evaporation tank and heated to 300 ° C by a substrate heating heater installed in the evaporation apparatus. A conductive antireflection film having a laminated structure shown in the column of Example 1 in Table 1 was coated on a glass plate. The evaporation material was evaporated by the 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 vacuum degree before the start of vapor deposition was exhausted to 0.003 Pa with an oil diffusion pump for all films. Nickel-iron alloy films, praseodymium titanate films, magnesium oxide films, and magnesium fluoride films 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. In addition, 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. The reflectance 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. In addition, the sheet resistance was 282 Ω square, which is low enough to have an antistatic function, and the resistance did not deteriorate (increase) even after being subjected to heat treatment, but rather decreased. Furthermore, the transmittance was only a small change of 0.7% from 66.5% to 67.2% .c This value was used by sticking it to the faceplate of a cathode ray tube or a transparent faceplate. From the practical point of view, the useful transmittance was in the range of 40 to 80% for the front glass panel.

Example 2 to Example 10

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

Example 4 is a film obtained by adding a base film of praseodymium titanate to the film structure of Example 2, and Example 7 is a film obtained by adding a base film of praseodymium titanate to the film structure of Example 6. 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.

Example Film 1 Film 2 Film 3 Film 4 Film 5 Film 6 Metal film composition

1 NiFe PrTi0 ₃ MgO MgF ₂ Fe / Ni

(3.2) (127.4) (45.4) (71.7) 20/80

2 NiFe PrTi0 ₃ MgO MgF ₂ ie / Ni

(3.2) (127.4) (45.4) (71.7) 10/90

3 NiFe PrTi0 ₃ MgO MgF ₂ Fe / Ni

(3.2) (127.4) (45.4) (71.7) 30/70

_{_{4 PrTi0 3 NiFe PrTi0 3 MgO MgF}} 2 Fe / Ni

(5.0) (2.0) (101.4) (36.3) (80.8) 20/80

_{_{_{5 PrTi0 3 NiFe PrTi0 3 MgF 2}}} Fe / Ni

(5.0) (3.2) (134.5) (96.8) 50/50

6 NiFe PrTi0 ₃ NiFe PrTi0 ₃ MgF ₂ Fe / Ni

(4.6) (26.0) (2.4) (35.0) (79.0) 20/80

7 MgO NiFe PrTi0 ₃ NiFe PrTi0 ₃ gF ₂ Fe / Ni

(5.0) (4.6) (26.0) (2.4.) (35.0) (79.0) 40/60

8 Pr i0 ₃ NiFe PrTi'J ₃ Fe / Ni

(5.0) (2.2) (34.8) (93.6) 95/5

_{_{_{9 PrTi0 3 NiFe PrTi0 3 MgF 2}}} Fe / Ni

(5.0) (2.4) (34.8) (93.6) 5/95

1 0 NiFe PrTi0 ₃ MgF ₂ Fe / Ni

(3.2) (34.8) (93.6) 5/95 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. Table 2 Transmittance (%) Reflectance (%) Sheet resistance (Ω / port) 刖 Difference after difference m Difference after m 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: After heat treatment Difference is after heat treatment and before heat treatment Comparative Example 1

A comparative sample was obtained in the same manner as in Example 1 except that the metal film was a film having a single composition of nickel, and the conductive antireflection film having the laminated structure shown in the column of Comparative Example 1 in Table 3 was coated in the same manner as in Example 1. 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 had a reflectance of 1% or less and good thermal stability of transmittance, but the sheet resistance was 2 M (mega) Ω / b or more both at the initial stage and after heat treatment. No antistatic function could be obtained. '

Comparative Example 2

A comparative sample was obtained in the same manner as in Example 1 except that the metal film was a film having a single composition of iron, and the conductive antireflection film having the laminated structure shown in the column of Comparative Example 2 in Table 3 was coated in the same manner as in Example 1. This ratio The results of evaluation of the 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 was as low as 0.43%, but the heat treatment increased the transmittance to 18.7% and the reflectance to 4.08%. In addition, 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 comparative sample of a laminated structure 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 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 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. However, the sheet resistance was 2M (mega) Ω or more both at the initial stage and after the heat treatment, and the antistatic property was good. Did not get the function.

Comparative Example 4 and Comparative Example 5

Using the metal film as 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 in the same manner 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 c chromium was obtained by heat treatment for transmittance. The change was increased by 9.8%, and Comparative Sample 5 containing 16% of chromium was found to increase by 9.2%, and the thermal stability was significantly deteriorated. It was also recognized that the heat treatment 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 exactly the same manner as in Comparative Example 1 except that the metal film was a two-component system of nickel and chromium. As shown in the column of Comparative Example 6 in Table 4, in this comparative sample, the change in the transmittance due to the heat treatment was as large as 12.5%, and the sheet resistance was increased by three orders of magnitude. Table 3

Table 4 Transmittance (%) Reflectivity (%) Sheet Resistance (Ω / port) Example 刖比較 Comparative 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 after heat treatment-Before heat treatment The value of the As described above, none of the comparative samples had stable characteristics in terms of transmittance and sheet resistance to heat treatment. In contrast, in the sample of the example of the present invention, 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. It is understood that it is done.

In a display device such as a cathode ray tube that displays a phosphor by irradiating the phosphor with an electron beam at an accelerated rate, the conductive performance of the conductive anti-reflection film with antistatic function provided on the front of the image display section is approximately lk Q / CI or less, and preferably about 500 Ω / b or less in order to have the ability to block radiated 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, when the metal film of the antireflection film composed of the laminate of the metal film and the transparent dielectric film is formed of a single film of nickel or a single film of iron, they are subjected to a heat treatment. Surprisingly, this was achieved by experimentally finding the expected I ヽ effect of improving the stability of electrical resistance by using nickel and iron alloy films. Things.

Since the metal film constituting the conductive anti-reflection film of the present invention was formed of a nickel-iron alloy film, the conductive anti-reflection film had excellent thermal stability. Therefore, even when subjected to a high-temperature heat treatment, changes in the transmittance and the reflectance are small. In addition, since the metal film of the conductive antireflection film is formed of a film of an alloy of nickel and iron, the sheet resistance is stable even when subjected to a high-temperature heat treatment. Industrial applicability

Since the optical properties and electrical resistance properties of the conductive anti-reflection film of the present invention are thermally stable, a glass face plate coated with the conductive anti-reflection film of the present invention is heated and joined with funnel and frit glass. However, 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.

Claims

The scope of the claims

1. On a glass substrate having a refractive index of 1.4 to 1.7 at a wavelength of 550 nm, in order from the glass substrate side, a first layer of a metal film and a second layer of a 550 nm wavelength. A high-refractive-index transparent dielectric film with a refractive index of 2.0 to 2.4 and a low-refractive-index transparent dielectric film with a refractive index of 1.35 to 1.46 at a wavelength of 55 Onm of the third layer are laminated. A glass article coated with the coated conductive anti-reflection film, wherein the metal film is a nickel-iron alloy film and the visible light reflectance is 1% or less. With glass articles.

2. The glass article with a conductive antireflection film according to claim 1, wherein the nickel content in the metal film is 5% by weight or more and 95% by weight or less.

3. Increase the thickness of the metal film to 1.5ηπ! The glass article with a conductive anti-reflection film according to claim 1 or 2, wherein the glass article has a thickness of from 8 to 8 nm.

4. Increase the thickness of the high refractive index transparent dielectric film of the second layer to 5 ηπ! The thickness of the low-refractive-index transparent dielectric film of the third layer is set to 50 nm to 120 nm.

A glass article with a conductive anti-reflection film according to any one of-

5. On a glass substrate having a refractive index of 1.4 to 1.7 at a wavelength of 550 nm, in order from the glass substrate side, a metal film of a first layer and a metal film of a second layer at a wavelength of 550 nm. A high-refractive-index transparent dielectric film having a refractive index of 2.0 to 2.4, and a medium-refractive-index transparent dielectric film of a third layer having a refractive index of 1.7 to 1.9 at a wavelength of 550 nm; A glass article coated with a conductive anti-reflection film on which a low-refractive-index transparent dielectric film having a refractive index of 1.35 to 1.46 at a wavelength of 55 Onm of the fourth layer is laminated, wherein the metal A glass material with a conductive anti-reflection film, characterized in that the film is a nickel-iron alloy film and the visible light reflectance is 1% or less.

PPo

6. The glass article with a conductive antireflection film according to claim 5, wherein the nickel content in the metal film is 5% by weight or more and 95% by weight or less.

7. The glass article with a conductive antireflection film according to claim 5, wherein the thickness of the metal film is 1.5 nm to 8 nm.

8. The thickness of the high refractive index transparent dielectric film of the second layer is 5 nm to 70 nm, and the thickness of the intermediate refractive index transparent dielectric film of the third layer is 10 ηπ! The conductive antireflection according to any one of claims 5 to 7, wherein the low-refractive-index transparent dielectric film of the fourth layer has a thickness of 50 nm to 120 nm. Glass article with film.

9. On a glass substrate having a refractive index of 1.4 to 1.7 at a wavelength of 55 Onm, the metal film of the first layer and the second layer at a wavelength of 55 Onm are sequentially arranged from the glass substrate side. A high-refractive-index transparent dielectric film having a refractive index of 2.0 to 2.4, a third metal film, and a fourth layer having a refractive index of 2.0 to 2.4 at a wavelength of 550 nm. A conductive anti-reflective coating consisting of a laminated refractive index transparent dielectric film and a low refractive index transparent dielectric film with a refractive index of 1.35 to 1.46 at a wavelength of 550 nm of the fifth layer was coated. A glass article, wherein at least one of the first layer metal film and the third layer metal film is a nickel-iron alloy film, and has a visible light reflectance of 1% or less. Glass article with a protective film.

10. The glass article with a conductive antireflection film according to claim 9, wherein the nickel content in the nickel-iron alloy film is 5% by weight or more and 95% by weight or less.

11. The thickness of the first and third layers of metal film varies 1.5 ηπ! The glass article with a conductive antireflection film according to claim 9 or 10, wherein the total thickness is 9 nm or less.

12. The thickness of the high refractive index transparent dielectric film of the second layer is 10 nm to 7 Onm, and the thickness of the high refractive index transparent dielectric film of the fourth layer is 10 ηπ! ~ 70 nm, 5th layer low refractive index transparent dielectric film with thickness of 7 誘電 ηπ! The glass article with a conductive anti-reflection film according to any one of claims 9 to 11, wherein the glass article has a thickness of from 120 to 120 nm.

13. The glass with a conductive anti-reflection film according to any one of claims 1 to 12, wherein a transparent dielectric film is provided between the glass substrate and the first metal film. Goods.

14. The glass article with a conductive anti-reflection film according to any one of claims 1 to 13, wherein the glass substrate is a glass face plate for a cathode ray tube.

15. A glass article with a conductive anti-reflection coating according to claim 14 A cathode ray tube obtained by heating and joining to a glass frit.