JP2001332197A - Cathode ray tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cathode ray tube with a reflection preventive film having high film strength and a low and stable surface resistance value effective for AEF prevention. SOLUTION: The outer surface of a face panel 1 is provided with a reflection preventive film 12 having a conductive layer 10 formed of metal particulates or metal compound particulates 10a and an upper layer 11 containing mainly silica (SiO2) laminated. The upper layer 11 contains a chelating agent for stabilizing and fixing the metal particulates or metal compound particulates constituting the conductive layer 10 as a lower layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cathode ray tube having an antireflection surface treatment film (antireflection film) having a high effect of preventing electromagnetic wave leakage on an outer surface of a front panel (face panel) of a faceplate.

[0002]

2. Description of the Related Art Generally, in a color cathode ray tube used for a TV cathode ray tube, a computer display, or the like, phosphor layers of blue (B), green (G), and red (R) are formed on the inner surface of a face panel by dots. The phosphors are arranged in a predetermined pattern such as a shape or a stripe, and these phosphors emit light of each color by the collision of an electron beam to display an image.

[0003] Since such a cathode ray tube is usually used in external light, an antireflection film formed by laminating a plurality of layers having different refractive indexes is provided on the outer surface of the face panel. That is, the lower layer closer to the face panel is a high refractive index layer, and the upper layer farther from the face panel is a lower refractive index layer, so that light reflected at the interface of each layer interferes with each other and cancels out. Have been.

Many proposals have been made to further improve various characteristics of a cathode ray tube having such an anti-reflection film.

That is, an electromagnetic wave (electric field) generated from the electron gun and the vicinity of the deflection yoke inside the cathode ray tube leaks and may adversely affect peripheral electronic devices and the human body. electric f
It is conceivable to reduce the surface resistance of the anti-reflection film formed on the outer surface of the face panel in order to prevent the occurrence of the anti-reflection (or the anti-reflection) of the face panel. Various surface treatment films have been developed as films.

For example, JP-A-61-118932,
No. 61-118946, JP-A-63-160140, etc.
Various surface treatment methods for preventing charging of the face panel have been disclosed. The antireflection film for the purpose of preventing AEF has a surface resistance value (sheet resistance measured according to JIS K-6911) of 1 × 10 ⁶ Since it is necessary to be Ω / sq or less, a conductive layer containing conductive fine particles of a metal oxide such as ITO (tin oxide doped with indium) is provided.

Further, in order to improve the contrast, a dye (coloring material) having a selective absorption in a visible wavelength range is also included in the surface treatment film.

[0008]

However, in a cathode ray tube having a surface-treated film containing a coloring material, the surface resistance of the surface-treated film increases, so that AEF cannot be sufficiently prevented. there were.

An antireflection film having a conductive layer containing colored conductive metal fine particles such as silver (Ag) has also been proposed. However, the conductive fine particles are not necessarily required to have a desired visible wavelength range (around 550 nm). Is not selectively absorbed, so that improvement in contrast cannot be expected much, and lacks weather resistance such as ultraviolet light resistance, moisture resistance, and chemical resistance, resulting in deterioration of film strength and increase in resistance value. There was a problem.

Further, since the conductive fine particles are fine particles, it is known that when a large voltage is applied, the fine particles move, that is, so-called migration occurs. Then, in order to prevent migration, a binder component such as silica (SiO ₂ ) is added to the conductive layer. However, in this method, the electric resistance of the conductive layer increases, so that a desired surface is added. The resistance value could not be obtained.

Further, the surface treatment film in which the conductive layer contains fine metal particles has a problem that the luminance of the blue phosphor is reduced due to the spectral transmittance of the fine metal particles.

The present invention has been made to solve these problems, and has a low surface resistance that is effective for AEF prevention and is stable with time, has a sufficient film strength, and furthermore has a spectral transmittance. It is an object of the present invention to provide a cathode ray tube having a surface treatment film capable of improving contrast by adjusting the rate.

[0013]

According to a first aspect of the present invention, there is provided a cathode ray tube, comprising: a translucent panel; an antireflection film disposed on an outer surface of the panel; A cathode ray tube including a phosphor layer disposed on an inner surface of the panel, wherein the antireflection film has at least one conductive layer containing at least one kind of metal fine particles or metal compound fine particles, and Immediately above the layer, silica (Si
A layer comprising O ₂ ) as a main component and a substance for stabilizing and fixing the metal fine particles or metal compound fine particles is provided.

A cathode ray tube according to a second aspect of the present invention is a second aspect of the invention.
In a cathode ray tube including a translucent panel, an anti-reflection film disposed on an outer surface of the panel, and a phosphor layer disposed on an inner surface of the panel, The prevention film has at least one conductive layer containing at least one kind of colored fine particles, and has silica (SiO ₂ ) as a main component immediately above the conductive layer, and has a spectral transmittance of the colored fine particles. It is characterized by having a layer containing a substance to be adjusted.

Further, according to a third aspect of the present invention, there is provided a cathode ray tube, comprising: a translucent panel; an antireflection film disposed on an outer surface of the panel; and an inner surface of the panel. At least one conductive layer, wherein the antireflection film includes at least one kind of metal fine particles or metal compound fine particles and at least one kind of colored fine particles. And, directly above the conductive layer, silica (SiO ₂ ) as a main component, and fixing the metal fine particles or metal compound fine particles.
It is characterized by comprising a layer containing a substance that stabilizes and further adjusts the spectral transmittance of the colored fine particles.

Hereinafter, the contents of the present invention will be described in more detail.

In the present invention, metal fine particles constituting the conductive layer include silver (Ag), palladium (Pd), gold (Au), ruthenium (Ru), iron (Fe), manganese (Mn), and tungsten (W). VI) such as zinc (Zn)
Fine particles composed of metals of groups B, VIIB, VIII, IB, and IIB can be mentioned. Examples of the fine particles of the metal compound include oxides, nitrates, acetates, benzoates, and bromines of the above-mentioned VIB to IIB metals. Fine particles of compounds such as acid salts, bromides, carbonates, chlorides, chromium oxides (chromates) and citrates (citrates), or conductive materials such as ITO and ATO (antimony-tin oxide) Oxide fine particles may be used. The average particle size of these fine particles is 5 to 400 nm, more preferably 10 to 200 nm. The use of particles having a particle size of more than 400 nm is not preferable because not only the light transmittance of the film is remarkably lowered, but also light scattering is caused by the particles, and the film becomes cloudy and the resolution is lowered.

Examples of the colored fine particles include general pigment fine particles and fine particles of a colored conductive oxide such as colored ITO or colored ATO. It is preferable to use fine particles having a particle size of 5 to 400 nm, more preferably 10 to 300 nm. Further, metal fine particles having a particle size in the range of 5 to 200 nm (for example, silver fine particles, gold fine particles, tungsten fine particles, and the like) can also be used as the coloring fine particles.

In the present invention, as a substance added to the upper layer of the conductive layer to stabilize and fix the above-mentioned fine metal particles or fine metal compound particles, a stable chelate compound (complex) coordinated to a metal or metal compound is used. Compounds having a polydentate ligand to be formed (chelating reagents) which do not decompose or evaporate at 100 to 250 ° C., which is the firing condition for surface treatment when coordinated, are exemplified. As such a chelating reagent, β-diketones such as acetylacetone can be used. Further, mercaptosilane having a mercapto group, which has the same effect only by coordination, and amines such as diethanolamine and triethanolamine can be used.

Further, in the present invention, the substance for adjusting the spectral transmittance of the colored fine particles is 550 to 6
Preference is given to using dyes or pigments having a maximum absorption in the visible wavelength range of 00 nm. Dyes having such selective absorption include, for example, acid rhodamine B, rhodamine B,
Kaynar, Milling Red 63W (trade name of Nippon Kayaku Co., Ltd.) and the like. Examples of the pigment include phthalocyanine blue, ultramarine blue, cobalt blue, and the like.

Note that, depending on the combination of the fine metal particles or fine metal compound particles and the compound coordinating therewith, the spectral transmittance may change before and after the coordination, and the combination is appropriately selected.

In the cathode ray tube of the present invention, the conductive fine particles
(Metal fine particles or metal compound fine particles) and / or
Or a conductive layer containing colored fine particles as a high refractive index layer,
Directly or through another layer, silica (Si
O_Two ) As a main component, and fix and secure the above-mentioned conductive fine particles.
And adjust the spectral transmittance of the colored particles.
A low-refractive-index upper layer containing
The anti-reflection film has a structure in which two or more such layers are laminated.
have. The lower conductive layer and SiO 2_Two The lord
The ratio of the thickness to the upper layer as a component is not particularly limited,
 1: 1 to 1:50, preferably 1: 1 to 1:10
It is desirable.

In the present invention, to form an antireflection film on the outer surface of the panel, the following wet method (wet method) is used.
It is desirable to adopt In this method, first, the aforementioned 1
The kind or two or more kinds of metal fine particles or metal compound fine particles are added to a solvent mainly composed of ethanol, 2-propanol or the like and sufficiently stirred to prepare a dispersion. Next, the obtained dispersion is applied to the outer surface of the face panel polished and washed with cerium oxide, directly or via another layer (underlayer), by spin coating, spray coating,
It is applied by a known method such as roll coating or bar coating to form a lower coating film.

Next, on the lower coating film, ethanol or
Dispersion containing 2-propanol or the like as a solvent, a silica alkoxide (alcoholate) as the main component, and a compound (chelating reagent) having a function of chelating metal or metal compound fine particles contained in the lower coating film. Apply the solution by spin coating, spray coating, roll coating,
It is applied by a known method such as bar coating to form an upper coating film. Here, when spin coating is used to form the upper coating film, a smoother film is formed, and high resolution is obtained.

Thereafter, the lower and upper coating films are simultaneously dried and cured or fired by heating the coating film in which the upper and lower two coating films are laminated. Thus, the conductive layer containing the conductive fine particles and the SiO ₂ An antireflection film is formed by laminating an upper layer mainly composed of For the upper layer, an alkylsilane derivative such as alkylsilane or fluoroalkylsilane, a silica coupling agent, silicone, etc.
By containing 0.01 to 20%, more preferably 1 to 5%, the film strength and weather resistance can be further improved.

In the present invention, the compound having a polydentate ligand (chelating reagent) contained in the layer immediately above the conductive layer reacts with fine metal particles or fine metal compound particles constituting the conductive layer to form a chelate compound ( Complex) to stabilize. The formed chelate is electrically stable,
Even when a voltage is applied, so-called migration that moves and shifts does not occur, and desired characteristics are stably maintained over time.

Since such an insulating substance is contained not in the conductive layer but in the upper layer, the electric resistance of the conductive layer does not increase and a low surface resistance is realized. Further, there is no decrease in film strength.

Further, depending on the combination of the metal or metal compound fine particles and the chelating reagent coordinating with the metal or metal compound fine particles, the spectral transmittance changes depending on the coordination. It is also possible to adjust the rate.

[0029]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a sectional view showing the structure of a color cathode ray tube according to one embodiment of the present invention.

As shown in the figure, this cathode ray tube has a translucent panel (face panel) 1 such as a glass panel.
And an envelope comprising a funnel 2 and a neck 3 integrally joined to the panel 1, and a phosphor screen 4 is provided on the inner surface of the panel 1. The phosphor screen 4 is a phosphor layer of each color of blue (B), green (G), and red (R) arranged and formed in a predetermined shape such as a stripe shape and a circular dot shape (not shown). And a light absorbing layer (black matrix) (not shown) that fills the gaps between these phosphor layers. In addition,
The phosphor layers of blue, green, and red are a blue light-emitting phosphor (ZnS: Αg, Al) and a green phosphor (ZnS:
Cu, Δl), a red phosphor (Y ₂ O ₂ S: Eu)
Are mixed and dispersed in pure water together with polyvinyl alcohol (PVA), ammonium bichromate (ADC), a surfactant, etc. (suspension).
Is applied and dried on the inner surface of the panel by a usual method.

Further, a shadow mask 5 having a large number of electron beam passage holes is disposed inside the phosphor screen 4 so as to face the phosphor screen 4, and the electron beam is placed in the neck 3 of the envelope. An electron gun 7 that emits an electron gun 6 is provided. Further, an inner shield 8 for shielding the electron beam 6 emitted from the electron gun 7 from an external magnetic field is disposed inside the funnel 2, and a deflection for deflecting the electron beam 6 by the generated magnetic field is provided outside the funnel 2. The device 9 is arranged.

In such a cathode ray tube, a conductive layer 10 made of metal fine particles or metal compound fine particles 10a, and silica (SiO ₂ ) as a main component, as shown in FIG. An anti-reflection film 12 having a structure in which an upper layer 11 is laminated is formed. The upper layer 11 contains a chelating reagent for stabilizing and fixing the metal fine particles or the metal compound fine particles 10 a constituting the lower conductive layer 10.

In the cathode ray tube of the embodiment constructed as described above, the antireflection film 12 stably realizes a low surface resistance value effective for preventing the generation of AEF, and also includes the antireflection film 12 in the upper layer 11. The chelating reagent is used for the conductive layer 1
Metal fine particles or metal compound fine particles 10 constituting 0
reacts with a to form a chelate compound (complex) and stabilizes, so that even if a voltage is applied, the metal fine particles or metal compound fine particles 10a do not move or migrate, so-called migration does not occur, and desired characteristics can be maintained over time. It is maintained stably.

Next, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the following examples.

Examples 1 to 12 A lower layer coating solution and an upper layer coating solution for forming an anti-reflection film were prepared as follows. First,
As the lower layer coating solution, Ag-Pd, Ag-Au , including a rate of 0.3% of the fine particles of the Ru or RuO ₂ (both average particle size 55～95Nm), further dispersing agent, ethanol dispersion containing water, etc. Was prepared.

The upper layer coating solution contains 1.0% of an alcoholate (alkoxide) of silica such as dimethyl silicate (dimethoxysilane) and diethyl silicate (diethoxysilane). A liquid containing the stabilizing reagent shown in the following Table in the ratio shown in the same table was prepared.

Next, the outer surface of the cathode ray tube face panel (17-inch panel) after assembly is buffed with cerium oxide to remove dirt, dust, oil, and the like. Apply by spin coating method, about 0.
An undercoating film having a thickness of 05 to 0.2 μm was formed. Next, an upper layer coating solution is applied on the lower layer coating film by a spin coating method to form a film having a thickness of about 0.05 to 0.2 μm, and the upper and lower layer coating films are baked at a temperature of 210 ° C. for 30 minutes. Then, a smooth surface treatment film (anti-reflection film) was formed.

Next, the inter-panel resistance of the surface-treated films obtained in Examples 1 to 12 was measured. Measurements were made by using special solder (Cerasolzer manufactured by Asahi Glass Co., Ltd.) to create terminals directly above the so-called register marks at the H end, which is the midpoint of both short sides of the panel, and the resistance between these terminals was measured with a tester. It was performed by measuring.

Further, the scratch strength was measured. In the measurement of scratch strength, when using a Rockwell hardness HRC 60 test needle and applying a load of about 19.6 N (3 kg weight) in the vertical direction and scratching, there is no visible mark on the film surface at all. The sample was judged to be A, and the trace was recognized by intense light but was not recognized by ordinary light, and B was judged. Furthermore, using SUV-W1 manufactured by Iwasaki Electric Co., Ltd.
UV irradiation was performed by irradiating ultraviolet rays (360 nm) at an irradiation density of 100 KJ / cm ^{2 at} ° C. The results of these measurements are shown in the lower columns of Tables 1 and 2.

[0041]

[Table 1]

[Table 2] As is clear from Tables 1 and 2, the surface treatment films (antireflection films) obtained in Examples 1 to 12 were all AEF.
In addition to having a low resistance value effective for prevention, it has sufficient film strength. Further, the resistance value hardly changes due to the irradiation of ultraviolet rays.

Further, in the surface-treated film obtained in the example, a change in the spectral transmittance also occurred, and an improvement in contrast was realized.

[0043]

As is apparent from the above description, according to the present invention, in addition to having sufficient film strength, the present invention is stable with no deterioration in characteristics against changes in environmental conditions and the like, and has a high AEF.
An antireflection film having a low resistance effective for prevention can be obtained, and a high-performance cathode ray tube can be realized.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a schematic configuration of a color cathode ray tube according to an embodiment of the present invention.

FIG. 2 is an enlarged sectional view showing a structure of an antireflection film in the cathode ray tube of the embodiment.

[Explanation of symbols]

1 ......... panel 4 ......... phosphor screen 5 ......... layer 12 mainly composed of a shadow mask 10a ......... metal particles or metal compound particles 10 ......... conductive layer 11 ......... SiO ₂ ......... Anti-reflective coating

Claims (3)

[Claims] 1. A translucent panel and an outer surface of the panel
An anti-reflection film disposed on the inner surface of the panel;
A cathode ray tube provided with a phosphor layer, wherein the antireflection film has at least one type of metal fine particles.
Or at least one conductive layer containing metal compound fine particles.
And silica (SiO 2) immediately above the conductive layer. _Two) Mainly
Component, the metal fine particles or metal compound fine particles
Features a layer containing a substance that stabilizes and fixes
And a cathode ray tube. 2. A cathode ray tube comprising: a translucent panel; an antireflection film disposed on an outer surface of the panel; and a phosphor layer disposed on an inner surface of the panel. The film has at least one conductive layer containing at least one kind of colored fine particles, and has silica (SiO ₂ ) as a main component immediately above the conductive layer, and adjusts the spectral transmittance of the colored fine particles. A cathode ray tube comprising a layer containing a substance to be converted. 3. A cathode ray tube comprising: a translucent panel; an antireflection film disposed on an outer surface of the panel; and a phosphor layer disposed on an inner surface of the panel. The film has at least one conductive layer each containing at least one kind of metal fine particles or metal compound fine particles and at least one kind of colored fine particles, and silica (SiO ₂ ) is formed directly on the conductive layer. A cathode ray tube comprising a layer containing, as a main component, a substance that fixes and stabilizes the metal fine particles or metal compound fine particles and further adjusts the spectral transmittance of the colored fine particles.