JP3196227B2 - Cathode ray tube and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention can easily obtain a wide range of optical characteristics, can effectively prevent high-contrast, electrostatic induction-induced panel charging, and has a high mechanical and chemical strength and has a high optical strength. And a method of manufacturing the same.

[0002]

2. Description of the Related Art As means for simultaneously satisfying both a so-called antistatic function and a high-contrast function of a displayed image, which rapidly bring the charge generated by electrostatic induction when a switch of a cathode-ray tube power supply blinks to ground, the inventors of the present invention disclose the present invention. First, a method of forming a colored transparent conductive film on the panel surface has been proposed (Japanese Patent Application No. 1-145325).

That is, for example, an organic dye and at least one selected from tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), and antimony oxide (Sb ₂ O ₃ ), which have conductivity themselves, are used. After applying an alcohol solution containing ethyl silicate to the outer surface of the panel,
A method for forming a colored transparent conductive film by firing at a temperature of about 0 to 200 ° C. has been proposed.

[0004] Here, the above coating solution is first made of SnO ₂ ,
At least one selected from In ₂ O ₃ and Sb ₂ O ₃
A solution comprising a seed, ethyl silicate that forms a silica sol by a dehydration condensation reaction after a hydrolysis reaction, a mixed solvent such as an alcohol and a ketone, and water and an acid catalyst is prepared, and an organic solution such as an azo dye or an anthraquinone dye is formed in the solution. One or two of the dyes that can provide the desired optical properties
It was prepared by adding more than one kind, and the coating method was any of spin coating, dip coating and spray coating.

[0005] However, the above technique has the following problems. That is, when the transparent conductive film is colored with an organic dye, a film having a desired absorption curve can be easily obtained with a small addition amount of 1% by weight or less, and high contrast can be achieved. When exposed to a solvent or the like, fading is easily accelerated. In particular, it fades in about one hour at high temperatures, for example when placed in boiling water. In practice, it is assumed that the temperature may become high and high during storage of products, shipping and transportation, and the like. Therefore, it has been a problem to improve the water resistance and chemical resistance of this film.

[0006] After or simultaneously with the application of the solution for forming the colored transparent conductive film, the application of the solution for forming the anti-reflective surface protective layer mainly containing an alcohol solution containing ethyl silicate, Since the surface is unstable and in an active state, there has been a problem that the coloring dye and other components are eluted and exude to the antireflection surface protective layer.

In particular, the solution for forming the anti-reflection surface protective layer contains a large amount of alcohol, water and the like and has a low viscosity.
The dye and the like in the colored transparent conductive film applied first tended to elute. When such elution occurs, there is a disadvantage that the dye is discolored when the surface of the cathode ray tube is wiped with a solvent or the like, and optical characteristics are changed.

Further, the organic dyes used in the above-mentioned prior art require practical improvement in terms of chemical durability and optical durability.

[0009]

SUMMARY OF THE INVENTION One of the objects of the present invention is to solve the problems of the above-mentioned technology, to obtain a wide range of optical characteristics easily, to obtain a high-contrast panel by electrostatic induction. An object of the present invention is to provide a cathode ray tube which can prevent electrification, has high mechanical and chemical strength, and has stable optical characteristics, and a method for manufacturing the same.

Another object of the present invention is to solve the above-mentioned problems of the prior art and to further improve the contrast by simultaneously absorbing the intermediate colors of magenta and cyan to further improve the color purity. It is an object of the present invention to provide a cathode ray tube capable of displaying a clearer image and a method of manufacturing the same.

[0011]

According to the present invention, (1)
(A) (a) at least one organic dye, (b) conductive tin oxide, conductive indium oxide on at least a part of the outer surface of the face plate of the cathode ray tube;
At least one metal oxide selected from the group consisting of conductive antimony oxide and (c) silica
A cathode ray tube having a layer including a colored transparent conductive region made of gel and (B) an antireflection region mainly made of silica gel; (2) (A) at least an outer surface of a face plate of the cathode ray tube; (C) at least one kind of organic dye; (b) at least one kind of metal oxide selected from the group consisting of conductive tin oxide, conductive indium oxide, and conductive antimony oxide; A) applying an alcohol solution containing an alkyl silicate, (d) water and (e) an acid catalyst;
A method for producing a cathode ray tube, comprising: a step of applying an alcohol solution containing an alkyl silicate to the laminate obtained in the step (b); and (C) a step of heating and drying the laminate obtained in the step (B). And (3) (A) at least a part of an organic dye, (b) conductive tin oxide, conductive indium oxide, conductive at least on a part of an outer surface of a face plate of a cathode ray tube. At least one metal oxide selected from the group consisting of antimony oxides having: (c) an alkyl silicate,
(D) a step of applying an alcohol solution containing water and (e) an acid catalyst, (B) a step of applying heated steam to the surface of the laminate obtained in the step (A), and (C) a step of (B) Applying an alcohol solution containing an alkyl silicate to the laminate obtained in the step (D), and (D)
A method of manufacturing a cathode ray tube including a step of drying the laminate obtained in the step (C).

[0012]

According to the present invention, (A) (a) at least one organic dye (b) conductive tin oxide, conductive indium oxide, and conductive After forming at least one metal oxide selected from the group consisting of antimony oxide and (c) a colored transparent conductive region mainly composed of silica gel, (B) an antireflection region mainly composed of silica gel is formed. Since the layer containing the color cathode ray tube is formed, it is possible to obtain a color CRT having stable antistatic properties, light wavelength selective absorption properties and antireflection properties.

In the above structure, the organic dye of the first layer has a role of giving selective absorption characteristics, the conductive metal oxide has a role of antistatic, and the silica gel of the first layer has a role of combining the organic dye with the organic dye. It has a role of bonding the conductive metal oxide and bonding to the face panel. Further, the silica gel of the second layer has a role of antireflection and protection of the first layer.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The cathode ray tube of the present invention has a colored transparent conductive region (hereinafter referred to as Co) on at least a part of the face plate surface.
lored Transparent Electroconductive Domain, abbreviated as CTE area) and anti-reflection area (hereinafter Non-Gl
are abbreviation of are Protective Domain).

The CTE region comprises at least one metal dye selected from the group consisting of (a) at least one organic dye, (b) conductive tin oxide, conductive indium oxide, and conductive antimony oxide. And (c) mainly silica gel. The CTE region may be in the form of a film, a disk, or a ring.

The type of the organic dye is not particularly limited. Preferably, among the acid dyes, cationic dyes, reactive dyes, direct dyes and disperse dyes, those having high light resistance and chemical resistance are used. Specifically, fluorescein sodium, rhodamine, oil blue, oil violet, acid rhodamine B (Acid Rhodamine B), Alizarin Direct Blue AGG
Is mentioned. These may be used alone or in combination of two or more.

In order to further improve the contrast, both the magenta color (wavelength around 560 to 580 nm) and the cyan color (wavelength 480 to 500 nm) of the emission spectrum of the phosphor among the organic dyes are used. Of the dyes that can simultaneously absorb and selectively absorb
It is also effective to use it by adding it to a solution for forming the E region.

In this case, two or more film-like CTE regions containing organic dyes having different wavelength absorption characteristics may be stacked.
Further, two or more organic dyes having different wavelength absorption characteristics may be contained in one film-like CTE region. Further, a film-like CTE region containing one organic dye and a film-like CTE region containing two or more organic dyes may be overlapped.

By providing the film-like CTE region with the selective absorption of two colors of magenta and cyan, an effect can be obtained in which the light color tone on the long wavelength side is well-sunk and clear by the conventional magenta color absorption elimination. In addition to the above, blue-green is eliminated by cyan color absorption, and blue and green can clearly appear.

In addition, by using the above-mentioned dye as an organic dye, a cathode ray tube having sharp wavelength absorption characteristics, and having excellent light resistance and chemical stability can be obtained.

The amount of the organic dye contained in the CTE region is not particularly limited. Usually, it is at most 1% by weight with respect to a CTE region forming solution described later.

The metal oxide contained in the CTE region is at least one metal oxide selected from the group consisting of conductive tin oxide, conductive indium oxide, and conductive almonium oxide.

The shape and size of the metal oxide are not particularly limited. Usually, a diameter of less than the wavelength of visible light is used, preferably a diameter of 100 nm or less, more preferably 50 nm or less, most preferably 10 nm or less.

The amount of metal oxide contained in the CTE region is
There is no particular limitation. Usually, when a cathode ray tube is used, 1
It is added so as to have a resistance of 0 ² -10 ¹¹ Ω / cm ² .

The aggregate state of silica gel mainly contained in the CTE region is not particularly limited. Fine particles, a uniform layer, or a mixed state thereof are preferred.

There are the following two methods for producing the cathode ray tube of the present invention.

(1) (A) At least a part of an organic dye, (b) conductive tin oxide, conductive indium oxide, conductive At least one metal oxide (C) selected from the group consisting of antimony oxide
(D) a step of applying an alcohol solution containing water and (e) an acid catalyst; and (B) alkyl on the laminate obtained in the step (A). (2) a method for producing a cathode ray tube including a step of spray-coating, spin-coating or dip-coating an alcohol solution containing silicate; and (C) a step of heating and drying the laminate obtained in the step (B). (A) At least a portion of an outer surface of a face plate of a cathode ray tube, (a) at least one organic dye, (b) conductive tin oxide, conductive indium oxide, conductive antimony oxide At least one metal oxide selected from the group consisting of (c) alkyl silicates (d) water and (e)
A step of applying an alcohol solution containing an acid catalyst,
(B) a step of applying heated steam to the surface of the laminate obtained in the step (A); (C) spraying and applying an alcohol solution containing an alkyl silicate to the laminate obtained in the step (B); A method for producing a cathode ray tube, comprising: a step of spin coating or dip coating; and (D) a step of drying the laminate obtained in the step (C).

First, the process (1) will be described.

In the process (1), the solution used for forming the CTE region is (a) at least one organic dye, (b) conductive tin oxide, conductive indium oxide, conductive At least one metal oxide selected from the group consisting of antimony oxide having
An alcohol solution containing (c) an alkyl silicate, (d) water and (e) an acid catalyst.

The types of the organic dye (a) and the metal oxide (b) are as described above.

Specific examples of the alkyl silicate (c) include:
Methyl silicate, ethyl silicate, n-propyl silicate, isopropyl silicate, n-butyl silicate, isobutyl silicate, sec-butyl silicate, tert-butyl silicate. Of these, methyl silicate and ethyl silicate are preferred, and ethyl silicate is more preferred.

The acid catalyst (e) is not particularly limited as long as it generates a hydronium ion when dissolved in water. Specific examples of the acid catalyst (e) include hydrochloric acid, nitric acid, acetic acid,
It is sulfuric acid.

The alcohol is not particularly limited as long as it is compatible with water. Specific examples of alcohols include methanol, ethanol, propanol, isopropanol, tert-butyl alcohol, allyl alcohol,
Ethylene glycol and glycerol.

The CTE region forming solution may contain trace amounts of ketones in addition to the above components.

The amount of the organic dye (a) contained in the CTE region forming solution is not particularly limited, but is usually at most 1% by weight.

The amount of the metal oxide (b) contained in the solution for forming the CTE region is not particularly limited, but is usually set so that the cathode ray tube has a resistance of 10 ² -10 ¹¹ Ω / cm ^2. Added.

The solution for forming the CTE region is obtained by mixing the above-mentioned components and stirring them so as to be uniform.

The method for applying the CTE region forming solution on the face plate is not particularly limited. Usually, spray coating, dip coating, and spin coating are used. According to the dip coating or the spin coating, of these methods, a film-like CTE region is formed. Further, according to the spray coating, a disk-shaped or ring-shaped CTE region is formed to overlap. Thus, a laminate in which the solution for forming the CTE region is applied on the face plate is obtained.

The solution used for forming the NGP region is an alcohol solution containing an alkyl silicate, water and an acid catalyst.

The types of the alkyl silicate, the alcohol, and the acid catalyst are as described above.

The amount of alcohol in the NGP region forming solution is not particularly limited, but is usually 40-95% by weight.
The composition of the alcohol is not particularly limited.
A composition of 9-85% by weight and 1-10% by weight of isopropanol is preferred. The amounts of the acid catalyst and water in the solution for forming the NGP region are not particularly limited, but are usually 2 to 50% by weight.

The amount of the alkyl silicate in the solution for forming the NGP region is not particularly limited, but is usually such that the amount of silica produced by the decomposition becomes 0.3 to 5.0% by weight.

The solution for forming the NGP region is obtained by mixing the above-mentioned components and stirring them so as to be uniform.

The method of applying the NGP region forming solution on the laminate having the CTE region forming solution applied on the face plate is not particularly limited. Usually, spray coating, dip coating, and spin coating are used. Here, the solution for forming the NGP region was applied to the CGP applied on the face plate.
It is preferable to apply the TE region forming solution so as to cover as much as possible. Note that, among these methods, according to dip coating or spin coating, a film-like NGP region is formed. Also, according to the spray coating, a disk-shaped N
An overlapping GP region is formed. Thereby, the solution for forming the CTE region and the N
A laminate to which the GP region forming solution has been applied is obtained.

The conditions for heating and drying the laminate on which the solution for forming the CTE region and the solution for forming the NGP region are applied on the face plate are not particularly limited. Preferably, 80
5-120 minutes at -250 ° C.

As described above, the cathode ray tube of the present invention is obtained.

Since the CTE region formed as described above is formed by a stable reaction product of alkyl silicate and an organic dye, an organic dye having desired optical characteristics can be selected and the amount of the organic dye to be added can be selected. A wide range of different colorings can be easily obtained simply by determining In addition, SnO ₂ , In ₂ O having conductivity itself
_Since a region containing at least one selected from ₃ and Sb ₂ O ₃ is formed, a stable and sufficient antistatic effect can be obtained.

In the cathode ray tube of the present invention, the above CT
Since the E region is mainly covered with the silica gel, the chemical durability and the mechanical durability are greatly improved. Silica is used as a conductive material such as SnO ₂ , S
It has a smaller refractive index than b ₂ O ₃ and In ₂ O ₃ (about 1.
4) Therefore, an antireflection effect is exhibited, which helps to control optical characteristics in a wide range. That is, the refractive index of the CTE region is in the range of 1.50 to 1.52, and when this is applied to the surface of the face plate (refractive index 1.52), the reflectance does not decrease and a glossy state is obtained. By coating with silica, the reflectance can be reduced.

Next, the process (2) will be described.

In the process (2), the solution used for forming the CTE region includes (a) at least one organic dye, (b) tin oxide having conductivity, indium oxide having conductivity, At least one metal oxide selected from the group consisting of antimony oxide having
An alcohol solution containing (c) an alkyl silicate, (d) water and (e) an acid catalyst.

The type and amount of each component contained in the CTE region forming solution are as described above.

The solution for forming the CTE region is obtained by mixing the above-mentioned components and stirring them so as to be uniform.

The method for applying the solution for forming the CTE region on the face plate is not particularly limited. Usually, spray coating, dip coating, and spin coating are used. This allows
A laminate in which the solution for forming the CTE region is applied on the face plate is obtained.

Next, heated steam is applied to the laminate on which the solution for forming the CTE region is applied on the face plate.

The temperature of the heated steam may be 30 ° C. Usually 30 ° C to 100 ° C.

In the above, C on the face plate
The reason for applying the steam to the surface after applying the TE region forming solution is to promote the hydrolysis and dehydration condensation reaction of the alkyl silicate by the following formula to form a strong silica (SiO ₂ ) film. Is to do.

Si (OR) ₄ + 4H ₂ O → Si (OH) ₄ + 4ROH (1) 2Si (OH) ₄ → 2SiO ₂ + 4H ₂ O (2) (R is an alkyl group) Immediately after the application of the CTE region forming solution of the composition, the above reaction has not sufficiently proceeded on the surface of the applied material, and the viscosity of the NGP region forming solution to be subsequently applied is low, so that the hydrolysis of the CTP region is performed. When the progress of the dehydration condensation reaction in contact with the NGP region forming solution in a poor state, the colored dye or the like will be eluted, as described above to promote hydrolysis, dehydration condensation reaction, stable SiO ₂ By applying the solution for forming the NGP region after forming the film, a combination of the CTE region and the NGP region which has no bleeding of the coloring dye and the like, has high mechanical and chemical strength, and is optically stable can be obtained. That it can.

The reason why the heating temperature range after the application of the CTE region forming solution is preferably 30 ° to 100 ° C. is as follows.
0 ° C is the lowest temperature that can be controlled throughout the seasons,
If the temperature is 100 ° C. or more, the fluidity of the solution for forming the NGP region is rapidly lost, so that the diffusion speed of the solution is slowed, the coating is likely to be insufficient, and the film surface may be rough.

As described above, the CT on the face plate
The solution for forming the E region is applied, and the CTE
A laminate in which the alkyl silicate in the region has been hydrolyzed is obtained.

The components of the solution used for forming the NGP region and the manufacturing method are as described above.

The method of applying the NGP region forming solution on the above-mentioned laminate is not particularly limited. Usually, spray coating, dip coating, and spin coating are used. Where NGP
The region forming solution is preferably applied so as to cover as much as possible the CTE region forming solution applied on the face plate. Note that, among these methods, according to dip coating or spin coating, a film-like NGP region is formed. Further, according to the spray coating, a disk-shaped ring-shaped NGP region is formed to overlap.
Thereby, a solution for forming the CTE region and a solution for forming the NGP region are applied on the face plate, and a laminate in which the alkyl silicate in the CTE region is hydrolyzed by the heated steam is obtained.

The conditions for heating and drying this laminate are not particularly limited. Preferably, 5-120 at 80-250 ° C.
Minutes.

As described above, the cathode ray tube of the present invention is obtained.

Hereinafter, the cathode ray tube and the method of manufacturing the same according to the present invention will be specifically described with reference to examples.

(Embodiment 1) FIG. 1 is a sectional view showing a schematic structure of an embodiment of a cathode ray tube according to the present invention, in which a colored transparent conductive region 8 (hereinafter referred to as CT) provided on the front surface of a face plate 2 is shown.
E region), an antireflection region 9 (hereinafter referred to as NGP region) of silica gel mainly coated on the conductive film 8, a phosphor 5 provided on the inner surface of the face plate 2, and aluminum deposited on the phosphor 5 This shows that the cathode ray tube 1 is composed of the funnel 3 and the like welded to the face plate 2 by the film 6, the shadow mask 7, and the frit glass 4.

Here, the procedure for forming the film-like CTE region 8 and the film-like NGP region 9 will be described as follows. That is, first, the front surface of the face plate 2 is cleaned using an abrasive such as cerium oxide (CeO ₂ ) and an alkaline detergent (manufactured by Henkel-Hakusui), and then SnO ₂ + Sb ₂ O ₃ and ethyl silicate , A mixed solution obtained by adding an organic dye to a solution comprising a mixed solvent (ethanol, IPA, other alcohols and ketones), water and an acid catalyst, using a spinner to uniformly apply the solution. Volume 10ml, spinner rotation speed 1
(00 rpm, time 1 minute) to form a film-shaped CTE region 8. Next, a solution for forming an NGP region having the composition shown in Table 1 was sprayed onto the film-like CTE region 8 (using a commercially available low-viscosity airless spray gun, a solution amount of 20 ml, and a solution amount of about 30).
(Seconds) to form a film-like NGP region 9. In addition, 15
By heating and drying at 0 ° C. for 30 minutes, strong film-like CTE regions 8 and film-like NGP regions 9 were obtained.

Hereinafter, a cathode ray tube was completed by a usual method.

(Examples 2 to 4) Except that the kind of the coloring dye used was changed as shown in Table 1, cathode ray tubes were produced in exactly the same manner as in Example 1.

Example 5 A cathode ray tube was produced in exactly the same manner as in Example 1 except that the method of forming the CTE region was spray coating.

Example 6 A cathode ray tube was produced in the same manner as in Example 5 except that the formation of the CTE region and the formation of the NGP region were simultaneously performed.

COMPARATIVE EXAMPLE 1 A comparative example 1 is a cathode ray tube according to the prior art which has the same CTE region as in Example 1, but does not wait for the NGP region as disclosed in the present invention.

The CTEs of the above Examples and Comparative Examples were
Liquid composition and coating method used to form the region, liquid composition and coating method used to form the NGP region, heating and drying conditions and properties of the resulting laminated face plate (color tone, gloss value, surface resistance, pencil strength, chemical Are shown in Table 1.

From the results shown in Table 1, it is clear that the cathode ray tubes of Examples 1 to 6 have a gloss value of 70 to 75% and a value of about 2 compared to Comparative Example 1.
It can be seen that the pencil strength and the chemical strength are greatly improved by 5 to 30%. When an image is actually displayed on a TV receiver, the external light reflectance (gloss value) is 25 to 3
The image was very easy to see because it was 0% smaller. The surface resistance value was 10 ⁷ Ω /
□, set these cathode ray tubes in the TV receiver,
As a result of measuring the decay time of the surface potential when the switch blinks,
It was found that it had a sufficient antistatic function. Also, the selective absorption of light in the CTE region cuts unnecessary light between the emission of the red, green, and blue phosphors, thereby improving the contrast, and improving the color purity, whereby the image is sharp. It turned out to look like. FIG. 2 shows an emission spectrum 10 of each of the red, green, and blue phosphors and a spectral selective absorption characteristic 11 in the CTE region in the above embodiment. From this figure, CTE
The selective absorption characteristics 11 of the region can selectively absorb the color (shown by oblique lines) in the middle part of the emission spectrum 10 of each phosphor, improving the color purity, lowering the dark color tone, and improving the contrast. Can understand well.

In the above-described embodiment, an example in which the coloring dyes are used alone has been described. However, different dyes may be mixed and used in consideration of the durability and the like according to the customer's preference. Is also possible.

[0075]

[Table 1]

(Embodiment 7) FIG. 1 is a cross-sectional view showing a schematic structure of a cathode ray tube manufactured by using the manufacturing method of the present invention. The CTE region 8 and CTE region provided on the front surface of the face plate 2 are shown.
NGP region (mainly silica gel) 9 coated on region 8, aluminum film 6 deposited on phosphor 5 provided on the inner surface of face plate 2, shadow mask 7,
This shows that the cathode ray tube 1 is composed of the funnel 3 and the like welded to the face plate 2 by the frit glass 4.

Next, the procedure for forming the CTE region 8 and the NGP region 9 mainly made of silica gel will be described. First, the face plate 2 of the completed cathode ray tube 1
The front surface of the polishing pad is made of an abrasive such as cerium oxide or (Henkel-
After cleaning with an alkaline detergent (manufactured by Hakusui), Sn
A mixed solution obtained by adding an organic dye to a solution composed of O ₂ + Sb ₂ O ₃ , ethyl silicate, a mixed solvent (same components as in Example 1), water and an acid catalyst is uniformly applied using a spinner (in this case, 14%). In order to manufacture a cathode ray tube, the solution dripping amount was 10 ml, the spinner rotation speed was 100 rpm, and the time was 1
Min) to form a CTE region 8. Next, the cathode ray tube was inserted into a furnace, and the surface of the face plate was heated to about 50 ° C.
The steam is fed into the furnace while preheated to
The plate surface was exposed to water vapor for about 5 minutes. Then, a solution for forming an NGP region having the following composition is applied to the surface of the face plate by spray coating, further inserted into a firing furnace, and dried by heating at 160 ° C. for 30 minutes to obtain a CTE region 8 and a NGP having a selective absorption function. A cathode ray tube having a region (mainly silica gel) 9 was completed.

Ethyl silicate: 2.5% by weight Ethanol: 55% by weight HNO ₃ , H ₂ O: 40% by weight Additive: 2.5% by weight Surface resistance is 1 × 10 ⁸ Ω
/ □, the gloss value according to the method specified in JIS Z8741 is 80%, there is no discoloration due to the wiping of the panel surface of the coloring dye that contributes to selective absorption, and the discoloration deterioration due to extraneous light (particularly ultraviolet light) is also based on the conventional technology. It was possible to obtain a cathode ray tube having less performance, a high contrast and a glare type having excellent performance.

Example 8 A CTE region was formed on the surface of a face plate of a cathode ray tube by the same procedure as in Example 7, and the face plate was preheated to 50 ° C. in a furnace and heated steam was applied thereto. NG of the same composition as in the case of 7
The solution for forming the P region is applied by spraying, and
For 2 minutes.

The laminate obtained in this manner was used in Example 7
Was a high quality laminate having exactly the same properties as in the case of

(Embodiment 9) After the same face plate surface treatment as in Embodiment 7 is performed using the same CTE region forming solution as in Embodiment 7, the solution is sprayed on the face plate surface. Was applied. Thereafter, a cathode ray tube having a CTE region and an NGP region was produced under exactly the same conditions as in Example 7.

Also in this case, the obtained laminate had a surface resistance value of 5 × 10 ⁸ Ω / □, a gloss value of 75% according to the method specified in JIS Z8741 and no discoloration of the dye was observed. A stable laminate was obtained.

Comparative Example 2 The CTE region and the NG under the same conditions as in Example 7 except that the heated steam was not brought into contact at the stage after the formation of the CTE region.
A P region was formed. In this case, the time from the formation of the CTE region to the formation of the NGP region is one time including the preheating.
0 minutes.

The laminate obtained in this manner is CTE
A phenomenon was observed in which the coloring dye in the region oozed out to the surface of the NGP region, and even after the heat-drying treatment, the dye was discolored when strongly wiped with ethanol. It was also measured that the fading due to sunlight or ultraviolet rays was about twice as fast as the samples of Examples 7 to 9.

Comparative Example 3 By the same procedure as in Comparative Example 2, except that the CTE region was formed and N
A cathode ray tube was prepared with a time interval between the formation of the GP region and a time interval of 2 hours and 24 hours.

For the cathode ray tube with a time interval of 2 hours, the discoloration was slightly improved, but was still insufficient.
Further, the color of the sample at a time interval of 24 hours does not completely disappear, but this condition is unsuitable in consideration of mass productivity.

Comparative Example 4 A laminate on a face plate when a cathode ray tube was prepared under the same conditions as in Example 7 except that the contact with heated steam was changed to spraying at room temperature by ultrasonic humidification, the discoloration was not observed. Although it improved somewhat, the result was that it could not be completely prevented yet.

(Embodiment 10) FIG. 1 is a partially cutaway drawing showing the configuration of one embodiment of the cathode ray tube of the present invention. In the drawing, reference numeral 1 denotes the entire cathode ray tube. An envelope is composed of a funnel 3 having a neck portion, and a frit glass 4 for hermetically sealing the funnel 3 and the face plate 2. 5 is a phosphor, 6 is an aluminum deposited film, and the deposited film 6 is a phosphor 5
Is formed on. Reference numeral 7 denotes a shadow mask, 8 denotes a CTE region formed on the outer surface of the face plate 2 by a method to be described later, and 9 denotes an NGP region which is formed on the CTE region 8. Here, the CTE region 8 was formed by the following steps.

First, after cleaning the outer surface of the face plate 2 of the cathode ray tube 1 shown in FIG. 1 (schematic sectional view of the cathode ray tube) in accordance with a predetermined washing procedure, the surface having the composition shown in the first column of Table 2 was applied. A solution for forming a CTE region containing an organic dye was applied by a spin coating method, and then heated and dried at 150 ° C. for 30 minutes to form a CTE region 8. In addition, the liquid components other than the dyes having the compositions shown in Table 3 were commonly used. The dye names in Table 2 are representative dye names in the dye table described in "Dye Handbook" (Maruzen Co., Ltd., issued on June 6, 1959). In addition, C.I. I. No indicates the color index No. described in the same book.

[0090]

[Table 2]

[0091]

[Table 3]

[0092]

[Table 4]

(Examples 11 and 12) The colored transparent conductive region 8 was formed in exactly the same manner as in Example 10 except that the solution for forming the colored transparent conductive region was changed to the composition shown in the second and third columns of Table 2. Formed.

Example 13 Exactly the same as Example 10 except that the solution for forming the colored transparent conductive region was a two-liquid composition having the composition shown in the fourth column of Table 2 and the colored transparent conductive region had a two-layer structure. Thus, a colored transparent conductive region 8 was formed.

Example 14 A colored transparent conductive region 8 was formed in exactly the same manner as in Example 10 except that the colored transparent conductive region was formed by spray coating.

Example 15 After the colored transparent conductive area 8 was formed in the same manner as in Example 10, a solution having the composition shown in Table 4 was applied on the area by spray coating to form the antireflection area 9. Formed.

(Example 16) A cathode ray tube having exactly the same structure as in Example 15 was prepared except that the application of the colored transparent conductive region was performed by the spraying method.

Comparative Example 5 A colored transparent conductive area 8 was prepared in exactly the same manner as in Example 10 except that the acid dye added to the solution for forming the colored transparent conductive area was only Acid Rhodamin B (Acid Rhodamin B). Was formed.

The results obtained for the characteristics such as color tone, chemical resistance, and optical resistance of the laminate on the face plate of each cathode ray tube prepared as described above are summarized in the lower part of Table 2. .

Here, the color tone refers to the B of the emission spectrum (blue B, green G, red R) of the cathode ray tube phosphor shown in FIG.
This indicates the degree to which an unnecessary intermediate color (cyan color) C between G and an unnecessary intermediate color (magenta color) M between C and R are erased and a clear image can be displayed. FIG. 4 shows the results of spectral transmittance curves (FIG. 3) obtained for each sample.

FIG. 4 shows the degree of deterioration of the spectral transmittance of the sample when the laminate on the face plate was immersed in boiling water and when the laminate was exposed to direct sunlight. As shown, A, 2
The case of 0% deterioration is indicated by B, and the case of 50% deterioration is indicated by C, in hours and days, respectively.

The following can be seen from the results in Table 2.

First, as for the color tone, the laminate on the face plate of the cathode ray tube of Comparative Example 5 shows a sufficient absorption for the M portion, but no absorption for the C portion, and the color purity of the blue portion of the image is unclear. In contrast, Examples 10 to 16
The laminate of the face plate of the cathode ray tube is M,
It can be seen that both C portions have sufficient absorption and have excellent optical characteristics.

Next, with respect to the chemical stability and light fastness, Comparative Example 5 showed slightly low chemical stability and fairly low light fastness. It is known that each of the laminates shows a high value, and particularly that the laminates of Examples 15 and 16 show a particularly high value. These results show that a mixture of two or more organic dyes has a synergistic effect on the strength, and that the presence of the antireflection region greatly contributes to the improvement of the strength.

[0105]

As described above, the cathode ray tube of the present invention and the manufacturing method of the present invention solve the problems of the prior art, and can easily provide a wide range and extremely stable optical characteristics. A cathode ray tube which has high contrast, prevents panel charging due to electrostatic induction, and further has antireflection performance, and a method of manufacturing the same.

Further, according to one embodiment of the cathode ray tube according to the present invention, the intermediate color of both the magenta and cyan colors in the phosphor spectrum is simultaneously selected and absorbed, so that the contrast of the image is further improved and the color purity is improved. Thus, a cleaner image can be shown.

Further, from the viewpoint of manufacturing, from the formation of the colored transparent conductive film to the formation of the anti-reflection protective film, it took at least 120 minutes in the prior art, but 5 minutes or less, that is, about 1 minute.
/ 20 or less, and a great effect was obtained in the mass production process.

[Brief description of the drawings]

FIG. 1 is a partially cutaway front view showing a schematic configuration of one embodiment of a cathode ray tube of the present invention.

FIG. 2 is a diagram showing emission spectra of red, green, and blue phosphors and selective absorption characteristics of visible light in a colored transparent conductive region.

FIG. 3 is an initial spectral transmittance curve of a colored transparent conductive region in Examples and Comparative Examples.

FIG. 4 is a diagram showing a change over time of a spectral transmittance line of a colored transparent conductive region in Examples and Comparative Examples.

[Description of Signs] 1 ... Cathode tube, 2 ... Face plate, 3 ...
・ Funnel, 4 ・ ・ ・ Frit glass, 5 ・ ・ ・ Phosphor, 6 ・ ・ ・ Aluminum deposited film, 7 ・ ・ ・ Shadow mask, 8 ・ ・ ・ Colored transparent conductive film area, 9 ・ ・ ・ Anti-reflection area ········ Emission spectrum of phosphor, 11 ···
・ Selective absorption characteristics of colored transparent conductive area

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kiyoji Miura 3300 Hayano Mobara-shi, Chiba Inside the Mobara Plant, Hitachi, Ltd. In the factory (72) Inventor Shunichi Asakura 3300 Hayano Mobara-shi, Chiba Pref. In the Mobara factory, Hitachi Co., Ltd. (56) References JP-A-1-286240 (JP, A) JP-A-3-11532 (JP, A JP-B-48-33549 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01J 29/88 H01J 9/20

Claims (13)

(57) [Claims] At least a portion of an outer surface of a face plate of a cathode ray tube comprises (A) (a) at least one organic dye, (b) conductive tin oxide, conductive indium oxide, and conductive. At least one metal oxide selected from the group consisting of antimony oxides having
A colored transparent conductive region mainly composed of silica gel,
(B) mainly have a anti-reflection region made of silica gel, the antireflection region on the colored transparent conductive region
The cathode ray tube that provided. 2. The cathode ray tube according to claim 1, wherein the colored transparent conductive region (A) is a continuous layer, and the antireflection region (B) provided thereon has a disk-like or ring-like overlap. . 3. The layer of colored transparent conductive region (A) is disc-shaped or
2. The cathode ray tube according to claim 1 , wherein each has a ring-like overlap, and the antireflection region (B) provided thereon is a continuous layer. 4. The layer of colored transparent conductive region (A) is disc-shaped or
2. The cathode ray tube according to claim 1, wherein each has a ring-like overlap, and the antireflection area (B) provided thereon has a disk-like or ring-like overlap. 5. The colored transparent conductive region has a wavelength of 560-580.
2. The cathode ray tube according to claim 1, which selectively absorbs light in the vicinity of nm and light in the wavelength of 480-500 nm. 6. The cathode ray tube according to claim 1, wherein the silica gel is mainly an aggregate of film and / or fine particles. 7. The cathode ray tube according to claim 1, wherein the metal oxide has a particle diameter of 100 nm or less. 8. (A) At least a part of an outer surface of a face plate of a cathode ray tube, (a) at least one organic dye, (b) conductive tin oxide, conductive indium oxide, conductive Applying at least one metal oxide selected from the group consisting of antimony oxide having (c) an alkyl silicate, (d) water and (e) an alcohol solution containing an acid catalyst, (B) the step (B) A step of applying heated steam to the surface of the solution applied in A), (C) film-like coloring obtained in the above step (B)
A method for producing a cathode ray tube, comprising: a step of applying an alcohol solution containing an alkyl silicate to a conductive region ; and (D) a step of drying the laminate obtained in the step (C). 9. The method according to claim 8 , wherein the temperature of the heated steam is 30 ° C.-100 ° C. 10. The method of claim 8 wherein the alkyl silicate is ethyl silicate. 11. The method according to claim 8 , wherein the acid catalyst is at least one selected from the group consisting of hydrochloric acid, nitric acid, acetic acid, and sulfuric acid. 12. The method according to claim 8 , wherein the alcohol is a mixture of ethanol and isopropanol. 13. The method of application includes spray coating, dip coating,
9. The method of claim 8 , wherein the method is any of spin coating.