CN1020223C - Cathode-ray tube and process for producing same - Google Patents
Cathode-ray tube and process for producing same Download PDFInfo
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- CN1020223C CN1020223C CN 91103125 CN91103125A CN1020223C CN 1020223 C CN1020223 C CN 1020223C CN 91103125 CN91103125 CN 91103125 CN 91103125 A CN91103125 A CN 91103125A CN 1020223 C CN1020223 C CN 1020223C
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Abstract
A cathode-ray tube having a layer provided on a face plate outer surface, with the layer comprising at least one colored transparent electroconductive domain consisting of at least one organic dye, at least one electroconductive metal oxide and silica mainly composed of silica gel and at least one non-glare and protective domain consisting of silica mainly composed of silica gel, thereby resulting an a cathode-ray tube having wide and stable optical properties, high contrast, and antistatic property to remove the panel electricity generated by static induction, and an antireflection property.
Description
The present invention relates to a kind of Braun Tude And Its Preparation Method, this cathode ray tube has wide and stable optical characteristics, high-contrast, removes the antistatic property of the electric charge that is produced by electrostatic induction and high machinery and chemical durability effectively on panel.
For making cathode ray tube have (a) because of switch connection or disconnect the ability that electric charge that caused electrostatic induction produces is transferred to ground rapidly, it is antistatic property, and (b) high image contrast, the inventor proposed a kind of method (Japanese patent application No.1-145325) that forms transparent colorful conductive film on the panel of cathode ray tube in the past.Also that is to say, the inventor had proposed a kind of method that forms the transparent color conducting film on the panel outer surface of cathode ray tube, this method be contain one or more organic dyestuff, at least a conducting metal oxide of from tin oxide (SnO2), indium oxide (In2O3) and antimony oxide (Sb2O3), selecting, and the alcoholic solution of silester be coated on the panel outer surface of cathode ray tube, and should surface heat drying under about 100 °-200 ℃ temperature.
In said method, the operation of preparation alcoholic solution is as follows: at first prepare a kind of solution, and this solution comprises at least a metal oxide selected, dewatered then when being subjected to hydrolysis from SnO2, In2O3 and Sb2O3-a kind of mixed solution, water and the acid catalyst that can form the silester of Ludox during condensation, be formed by alcohol, ketone etc.; Then providing required optical characteristics, at least a organic dyestuff of selecting from azo dyes, anthraquinone dye etc. to add solution.Utilize any method coating alcoholic solution in spin coating, dip-coating and the spraying.
, above-mentioned technology has following point.That is, when the transparent color conducting film contains quantity less to 1% weight or one or more organic dyestuff still less, just can demonstrate required optical absorption characteristic, and can provide high image contrast; Yet, when this conducting film be subjected to water, acid, alkali, organic solution etc. do the time spent tend to fade too early.Particularly under the high temperature, for example conducting film is put into boiling water, will fade after about one hour.Because expection adopts the appliances of described conducting film may be subjected to high temperature and high humility in processes such as storage, water transport, need to improve the water-resistance and the chemical resistance of conducting film.
In addition; also having a problem is to be applied on the panel earlier when forming the solution that the transparent color conducting film uses; thereafter or simultaneously when mainly being coated on the panel that the surface was coated with by forming of forming of the alcoholic solution that the contains silester solution that anti-dazzle sealer uses; coloured dye in the transparent color conducting film or other component can dissolve in or be diffused in the anti-dazzle sealer, because described conducting film surface instability is active again.
Because the solution that the anti-dazzle sealer of formation is used contains a large amount of alcohol, water etc., and viscosity is low, this solution tends to make the dissolvings such as dyestuff that are present in the transparent color conducting film.When having this dissolving, will remove dyestuff with the solvent cleaned surface of cathode-ray tube, the result is the optical characteristics deterioration that makes cathode ray tube.
In addition, the organic dyestuff that conventional method adopted is good inadequately aspect chemistry and optics durability, need be improved.
The objective of the invention is to solve the problems referred to above of prior art, and a kind of cathode ray tube is provided and the method for making this cathode ray tube is provided, this cathode ray tube has wide and stable optical characteristics, high-contrast, can remove the electric charge and high machinery and the chemical durability that are produced by electrostatic induction effectively on panel.
Another object of the present invention is to solve prior art problems, a kind of cathode ray tube is provided and the method for making this cathode ray tube is provided.This cathode ray tube can optionally absorb dark red (megenta) and dark green (cyan) these two kinds of middle color, thereby has good contrast, high color purity and more colored.
According to the present invention, provide:
(1) a kind of cathode ray tube that at least a portion of its panel outer surface, has the coating that contains following component:
(A) at least one transparent color conductive region, it comprises (a) at least a organic dyestuff, (b) at least a conducting metal oxide of selecting from tin oxide, indium oxide and antimony oxide (c) is mainly the silicon dioxide of silica gel form, and
(B) at least one anti-dazzle protection zone, it comprises the silicon dioxide that is mainly the silica gel form;
(2) a kind of method of making cathode ray tube, comprising the following step of being used to:
(a) coating contains the alcoholic solution of following component at least a portion of the panel outer surface of cathode ray tube: (a) at least a organic dyestuff, (b) at least a conducting metal oxide of from tin oxide, indium oxide and antimony oxide, selecting, (c) alkyl silicate (alkyl silicate), (d) water and (e) acid catalyst
(B) apply a kind of alcoholic solution that contains alkyl silicate on the panel surface that the surface applied that obtains is crossed in step (A), and
(C) the not dried overbrushing layer panel that is obtained carried out heat drying in step (B); And
(3) a kind of method of making cathode ray tube, comprising the following steps of being used to:
(A) a kind of alcoholic solution that contains following component of coating at least a portion of the panel outer surface of cathode ray tube: (a) at least a organic dyestuff, (b) at least a conducting metal oxide of from tin oxide, indium oxide and antimony oxide, selecting, (c) alkyl silicate, (d) water and (e) acid catalyst
(B) steam is added on the surface of the panel that the surface applied that obtained in the step (A) crosses,
(C) alcoholic solution that contains alkyl silicate being coated in the surface applied that is obtained in the step (B) has crossed and has applied on the surface of panel of steam.
(D) the not dried overbrushing layer panel that is obtained carried out heat drying in step (C).
Fig. 1 is the front view of partly cut-away of general configuration of an embodiment of expression cathode ray tube of the present invention.In Fig. 1, label 1 expression cathode ray tube; Label 2 expression panels; Label 3 expression pipe awls; Label 4 expression sintered glasses; Label 5 expression fluorescent materials; Label 6 expression deposit aluminium films; Label 7 expression shadow masks; Label 8 expression transparent color conductive regions; Label 9 expression anti-dazzle protection zones.
Fig. 2 is the radiation spectrum of red, the green and blue look fluorescence of expression and the selectivity absorption characteristic of transparent color conductive region.In Fig. 2, the radiation spectrum of label 10 expression fluorescent materials, wherein B, G and R represent orchid, green and red respectively; The selectivity absorption characteristic of label 11 expression transparent color conductive regions, wherein " a " represents embodiment 2, " b " expression embodiment 1,4,5,6 and comparing embodiment 1, " c " represents example 3.
Fig. 3 represents the initial spectrum transmittance curve of transparent color conductive region in each example and the comparative example.
Fig. 4 is the time dependent curve of spectral transmittance curve of transparent color conductive region in each example of expression and the comparative example.
Cathode-ray tube of the present invention has the coating that comprises at least one transparent color conductive region (hereinafter referred to as overscan area territory) and at least one anti-dazzle protection zone (hereinafter referred to as NGP zone) at least a portion of its panel outer surface.
The overscan area territory is comprised of following several component: (a) at least a organic dyestuff, at least a conducting metal oxide of (b) selecting from tin oxide, indium oxide and antimony oxide (c) is mainly the silica of silica gel form. The overscan area territory can be film-shaped, dish type or annular.
The kind of organic dyestuff is not subject to special restriction, but preferably chooses from acid dyes, the dye of positive ion, reactive dye, direct dyes and disperse dyes, and these dyestuffs have high-light-fastness and anti-chemistry. The object lesson of this class dyestuff comprises fluorescein sodium, rhodamine, blue, the oily purple of oil, acid rhodamine B, the direct blue AGG of alizarin (Alizarine), acid pale yellow 2G, acid red 3b1, sharp Su Pula (Siriius supra) orange GGL of sunset and reactive yellow E-SNA. They can use separately, and perhaps two or more mixes use.
In order to give good contrast, following method is effective: (a) choose the mixing of different dyes from above-mentioned organic dyestuff, this different dyes is mixed can optionally absorb the light with 560-600nm wavelength of launching from the fluorescent material that is coated on the panel inner surface and the light with 480-500nm wavelength simultaneously, and then (b) is mixed for described different dyes to form the solution in overscan area territory hereinafter described.
Mixing the different dyes of using can be present on the panel outer surface of cathode-ray tube by two-layer or two-layer above form, every one deck is to contain a kind of class film-form overscan area territory that the specific organic dyestuff of specific absorption characteristic is arranged, or with the form in the thin film shape overscan area territory that comprises at least two kinds of different organic dyestuff that different absorption characteristics are arranged, perhaps with two-layer form, one deck is the class film-form overscan area territory that contains a kind of organic dyestuff, and another layer is the class film-form overscan area territory of containing two or more organic dyestuff.
Having for wavelength by permission class film-form overscan area territory is the selective absorption characteristic of the light of 480-500nm and 560-600nm, the photochromic accent of longer wavelength side is than darker with conventional art, thereby can obtain distinct image, and by being that the Optical Absorption of 560-600nm is eliminated orchid-green to wavelength, thereby can clearly produce blue look and green.
Adopt that above-mentioned organic dyestuff further can obtain to have strong absorption characteristic, good light resistance and the cathode-ray tube of chemical stability.
The amount that is used for one or several organic pigments in overscan area territory is not subject to special restriction, 1% weight of the amount of the solution that it is normally used by the overscan area territory that forms hereinafter described or less.
The metal oxide that is used for the overscan area territory is at least a conducting metal oxide of selecting from tin oxide, indium oxide and antimony oxide.
Shape and size to metal oxide particle have no particular limits. , the diameter of metal oxide particle is not more than visible light wavelength usually, and it is better to be not more than 100nm, and it is better to be not more than 50nm, preferably then is to be not more than 10nm.
Amount to the metal oxide that is used for the overscan area territory has no particular limits. Yet metal oxide is normally for example to make the cathode-ray tube that is obtained have 105-10
11Ω/cm
2The amount of resistance use.
Form to the silica that is mainly the silica gel form that is used for the overscan area territory has no particular limits. It is preferably with particulate, the even form of thin layer or their mixture.
Any one that utilizes following two kinds of methods just can produce cathode-ray tube of the present invention.
(1) a kind of method for the manufacture of cathode-ray tube comprises following all steps:
(A) contain the alcoholic solution of following component at least a portion coating of the panel outer surface of cathode-ray tube: (a) at least a organic dyestuff, (b) at least a conducting metal oxide of from tin oxide, indium oxide and antimony oxide, selecting, (c) alkyl silicate, (d) water and (e) acid catalyst
(B) spraying on the surface of the panel crossed of the surface applied that in step (A), is obtained, spin coating or a kind of alcoholic solution that contains alkyl silicate of dip-coating, and
(C) the not dried overbrushing layer panel heat drying that in step (B), is obtained.
(2) a kind of method that is used to make cathode ray tube comprises following all steps:
(A) a kind of alcoholic solution that contains following component of coating at least a portion of the panel outer surface of cathode ray tube: (a) at least a organic dyestuff, (b) selected at least a conducting metal oxide from tin oxide, indium oxide and antimony oxide, (c) alkyl silicate, (d) water and (e) acid catalyst
(B) steam is added on the surface of the panel that the surface applied that obtained in the step (A) crosses,
(C) spraying on that cross and the panel that added steam of the surface applied that in step (B), is obtained, spin coating or a kind of alcoholic solution that contains alkyl silicate of dip-coating, and
(D) the not dried overbrushing layer panel that is obtained carried out drying in step (C).
Describing method (1) at first.
In method (1), the solution that is used for forming the overscan area territory is a kind of alcoholic solution that contains following component: (a) at least a organic dyestuff, (b) selected at least a conducting metal oxide from tin oxide, indium oxide and antimony oxide, (C) alkyl silicate, (d) water and (e) acid catalyst.
The kind of organic dyestuff (a) and metal oxide (b) is as indicated above.
The instantiation of alkyl silicate is methyl silicate, silester, silicic acid n-propyl, isopropyl silicate, the positive butyl ester of silicic acid, silicic acid isobutyl ester, silicic acid dibutyl ester and the silicic acid tert-butyl ester.In these alkyl silicates, methyl silicate and silester are better, and silester is better.
Acid catalyst (e) can be any acid, as long as can produce hydrogen ion when it is water-soluble.The instantiation of acid catalyst (e) is a hydrochloric acid, nitric acid, acetate and sulfuric acid.
Alcohol can be any alcohol, as long as it and water compatible.The instantiation of alcohol is a methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, the tert-butyl alcohol, allyl alcohol, ethylene glycol and glycerol.
Form the solution of using in the overscan area territory and can also comprise a small amount of ketone etc.
Amount to the organic pigment (a) of the solution that is used to form the overscan area territory has no particular limits, but is no more than 1% weight usually.
Amount to the metal oxide (b) of the solution that is used to form the overscan area territory has no particular limits, but used amount is to make that the cathode ray tube that is obtained has 10 usually
2-10
11Ω/cm
2Resistance.
Above-mentioned various components are mixed and stir and provide a kind of uniform solution and just can obtain the solution that formation overscan area territory is used.
The method that coating forms the solution in overscan area territory on the panel of cathode ray tube is not particularly limited, but adopt spraying usually, the method for dip-coating or spin coating.Dip-coating or spin coating form the overscan area territory of class film like, and spraying then forms the class plate-like that overlaps each other or the overscan area territory of class ring-type.The diameter of some of class plate-like or class ring-type overscan area territory is below 10 μ.Remaining diameter then is about 20 μ or 50 μ or more than 50 μ.This coating has provided the panel that a kind of surface applied is crossed, and the panel that applied comprises panel and is coated with and forms the solution that the overscan area territory is used thereon.
The solution that is used for forming the NGP zone is the alcoholic solution that contains alkyl silicate, water and acid catalyst,
The kind of alkyl silicate, alcohol and acid catalyst as mentioned above.
The amount that is used to form alcohol in the solution in NGP zone is not particularly limited, but accounts for the weight of 40-95% usually.The composition of alcohol is not particularly limited, but preferably is made up of the ethanol of 39-85% weight and the Probucol of 1-10% weight, and the acid catalyst and the water yield that form the solution in NGP zone are not particularly limited, but are generally 2-50% weight.
The amount that forms the solution mesosilicic acid Arrcostab of NGP zone usefulness is not particularly limited, but according to counting 0.3-5.0% weight by decomposing the silicon dioxide that is produced.
Provide the solution that a kind of uniform solution just can obtain to form NGP zone usefulness by said components being mixed and stirring.
The method that coating forms the solution in NGP zone on panel that surface applied the is crossed surface of (comprising panel and the solution in the formation overscan area territory that scribbles thereon) is not particularly limited, but adopt spraying usually, the method for dip-coating or spin coating.Preferably so apply the solution that forms the NGP zone, promptly will cover and apply the entire portion that forms the solution in overscan area territory on the panel.Dip-coating or spin coating form class film like NGP zone, and spraying then forms class plate-like or the class cyclic n nitroso compound GP zone that overlaps each other.This coating has provided a kind of not dried overbrushing layer panel, the solution that this overbrushing layer panel comprises panel, the formation overscan area territory of coating on it is used and the solution of the formation NGP of coating zone usefulness thereon again.
To comprise panel, the solution used of formation overscan area territory of coating on it and more thereon the not dried overbrushing layer panel of the solution of the formation NGP of the coating zone usefulness condition of carrying out heat drying be not particularly limited but preferably under 80 ° of-150 ℃ of temperature heat drying 5-120 minute.
So just can obtain cathode ray tube of the present invention.
Include organic dye and from the stopping reaction product of alkyl silicate as the formed overscan area of above-mentioned method territory, therefore reach the amount that suitably determines them by the organic dyestuff of selecting simply to have needed optical characteristics, the overscan area territory just can produce the various colours of wide region.The overscan area territory also comprises at least a conducting metal oxide selected from SnO2, In2O3 and Sb2O3, so the overscan area territory can have stable and enough antistatic properties.
In cathode ray tube of the present invention, the silicon dioxide that the overscan area territory is mainly the silica gel form covers, thereby has the chemistry and the mechanical robustness of remarkable improvement.In addition, the refractive index of silicon dioxide (about 1.4) has anti-dazzle effect, and helps to control effectively optical characteristics less than as SnO2, the In2O3 of conductive materials and the refractive index of Sb2O3.That is be that the overscan area territory itself with 1.50-1.52 refractive index can not reduce the refractive index (1.52) of panel, and brings luster effect; Yet, cover the refractive index that the overscan area territory can reduce panel with silicon dioxide.
Follow describing method (2).
In method (2), the solution that is used to form the overscan area territory is a kind of alcoholic solution that contains following component: (a) at least a organic dyestuff, (b) at least a conducting metal oxide of from tin oxide, indium oxide and antimony oxide, selecting, (c) alkyl silicate, (d) water and (e) acid catalyst.
Be used to form the overscan area territory solution component kind and the amount as mentioned above.
Said components mixed and stir and provide a kind of uniform solution just can obtain to form the solution that the overscan area territory is used.
The method that is used for applying the solution that forms the overscan area territory is not particularly limited, but adopt spraying usually, the method for dip-coating or spin coating.This coating has provided the panel that a kind of surface applied is crossed, and the latter comprises the solution that panel and the formation overscan area territory that is coated with are used thereon.
Then, steam is added on the panel that surface applied crosses.
The temperature of steam is not less than 30 ℃, is generally 30 °-100 ℃.
The reason that will be added in steam again after having scribbled the solution that forms the overscan area territory on the panel outer surface on the panel that the surface was coated with is the hydrolysis that will promote back to back alkyl silicate, and subsequent dehydration-condensation reaction, to form firm silicon dioxide (SiO2) film.
Wherein R is an alkyl.
After the solution that forms the overscan area territory was coated in the panel outer surface, on institute applying soln surface, above-mentioned reaction was not finished immediately.The solution of the formation NGP zone usefulness that then will be coated with simultaneously, has low viscosity.Therefore, contact with the solution that the formation overscan area territory of also fully not finishing above-mentioned reaction is used, will make that forming coloured dye in the solution of using in the overscan area territory etc. dissolves in the solution that forms the regional usefulness of NGP if form the solution in NGP zone.; quickening said hydrolyzed reaction, thereafter dehydration-condensation reaction; the result applies the solution that forms NGP zone usefulness after forming stable SiO2 film again; just can prevent slowly oozing out of coloured dye etc., and can obtain the compound of stable overscan area territory of machinery and chemical strength height, optical characteristics and NGP zone.
In this respect, make the solution that is added on the formation overscan area territory that is coated with steam temperature preferably 30 °-100 ℃ reason be, 30 ℃ is the minimum temperature that above-mentioned reaction can be controlled the whole year, and be higher than under 100 ℃ the temperature, the flowability that forms the solution in NGP zone greatly reduces, the spreading rate of solution reduces, thereby causes insufficient covering of solution in some cases and cause uneven film surface.
Therefore, added steam and will provide the panel that steam was crossed and added to a kind of surface applied, the alkyl silicate in the solution that the formation overscan area territory that wherein is coated with is used is hydrolyzed.
The preparation method who is used to form the component of solution in NGP zone and this solution as mentioned above.
The method that is used for the solution in coating formation NGP zone on the panel that be coated with and that be added with steam of above-mentioned surface is not particularly limited, but adopts the method for spraying, dip-coating or spin coating usually.Preferably be coated with the solution that forms NGP zone usefulness to such an extent that cover the solution in the formation overscan area territory that is coated with as far as possible fully.Dip-coating or spin coating form class film like NGP zone.Spraying then forms class plate-like or the class cyclic n nitroso compound GP zone that overlaps each other.So just can obtain a kind of not dried overbrushing layer panel, the solution that overbrushing layer panel comprises panel, is coated with the solution in formation overscan area territory thereon and is coated with formation NGP zone thereon again, the alkyl silicate that wherein forms the overscan area territory is because of applying the steam hydrolysis.
The condition of not dried overbrushing layer panel being carried out heat drying is not particularly limited, and heats 5-120 minute but be preferably under 80 ° of-250 ℃ of temperature.
So just can obtain cathode ray tube of the present invention.
Describe according to Braun Tude And Its Preparation Method of the present invention below by several examples.
Example 1
Fig. 1 is the sectional view of structure of an example of expression cathode ray tube of the present invention.In Fig. 1; cathode ray tube 1 comprises panel 2; be configured in the transparent color conductive region 8(overscan area territory hereinafter referred to as on panel 2 outer surfaces); the anti-dazzle protection zone 9(in covering overscan area territory 8 is the NGP zone hereinafter referred to as); be configured in the fluorescent material 5 on the inner surface of panel 2; be formed at the deposit aluminium film 6 on the fluorescent material 5, shadow mask 7 is with sintered glass etc. and the panel 2 pipe awl 3 of welding mutually.
The operation that forms class film like overscan area territory 8 and class film like NGP zone 9 is below described.At first, use the outer surface of crocus (for example cerium oxide (CeO2)) and alkaline cleaner (a kind of product of Henkel-plain boiled water society (Henkel-Hakusuisha)) clean face plate 2.Then, organic dyestuff is added in a kind of solution (this solution is made up of conductive materials (SnO2+Sb2O3), silester, mixed solvent (ethanol, IPA, other alcohol and ketone), water and acid catalyst), the mixed solution that is obtained is coated on the outer surface equably, forms class film like overscan area territory 8 with spinner.Make the cathode ray tube of 14 inches types, the amount of institute's applying soln is 10ml; The rotating speed of spinner is 100 rev/mins, and the coating time is 1 minute.Then, spraying forms the solution with component shown in the table 1 of NGP zone usefulness on class film like overscan area territory 8, to form the NGP zone 9 of class film like.In spraying process, adopt commercially available low viscosity air gun (solution amount that is coated with is 20ml, about 30 seconds of coating time).Then, heat drying is 30 minutes under 150 ℃ of temperature, has just obtained to have the panel in firm class film like overscan area territory 8 and firm NGP zone 9.
Thereafter common adopt identical in operation and this area, thus cathode ray tube made.
Example 2-4
Except used coloured dye is as shown in table 1 done to change, cathode ray tube be with example 1 in identical mode prepare.
Example 5
Overseas except form overscan area with spraying process, cathode ray tube be with example 1 in identical mode prepare.
Example 6
Except forming overscan area territory and NGP zone successively, cathode ray tube be with example 5 in identical mode prepare.
Comparative example 1
The cathode ray tube that has prepared a kind of prior art, this cathode ray tube have with example 1 in identical overscan area territory, but NGP zone as disclosed in the present invention not.
The cathode ray tube that is obtained in example 1-6 and comparative example 1 all lives through following various test.
(1) tone
The V-3200 of Hitachi type spectrophotometer measurement with Hitachi Ltd's production.
(2) gloss number
Measure according to the JIS Z of Japanese Industrial Standards 8741.
(3) sheet resistance
Measure with the TR-3 type high resistance tester that Tokyo Electronics Co., Ltd produced.
(4) pencil intensity (Pencil Strength)
Measure according to the JIS K of Japanese Industrial Standards 5401.
(5) chemical strength
Be immersed in film that its colour fades to 1/2 time representation in the boiling water.
The result of table 1 expression example 1-6 and comparative example 1, that is be, be used to form the component and the coating method of the solution in overscan area territory, be used to form the component and the coating method of the solution in NGP zone, heat drying condition, and the various characteristics of the overbrushing layer panel that obtain (tone, gloss number, sheet resistance, pencil intensity, chemical strength).
* its colour faded to 1/2 o'clock time in film immersion boiling water
Table 1 has proved that the gloss number of cathode ray tube of example 1-6 and the gloss number of comparative example 1 relatively are 70-75%, little about 25-30%, and demonstrating tangible improvement aspect pencil intensity and the chemical stability (Chemical Strength).When each cathode ray tube among the example 1-6 is assembled into when checking image in the television set, because less external light reflection rate (gloss number has been reduced 25-30%), it is very comfortable that image seems.The sheet resistance that each cathode ray tube among the example 1-6 has is 10
7Ω/ when each cathode ray tube is assembled into surface potential decay time when coming the measuring switch on-off in the television set, shows gratifying antistatic property.
In addition when the cathode ray tube of example 1-6 is assembled in the television set, utilize the selective light in overscan area territory to absorb and eliminated from unnecessary part red, green and the light that blue fluorescent material is launched, this has just provided the colorimetric purity of the contrast of improving, improvement and image clearly.The radiation spectrum 10 of red, green and blue fluorescent material and the selective light absorption characteristic 11 in the overscan area territory among the example 1-6 have been shown among Fig. 2.The selective light absorption characteristic 11 that from Fig. 2, can fully understand the overscan area territory optionally eliminated fluorescent material radiation spectrum 10 middle color (representing) with oblique line thus the contrast that has provided the colored of the colorimetric purity of improving, intensification and improved.
In in example 1-6 each, adopt single coloured dye, but also can adopt the different dyes of mixing according to hobby of client etc. and the life-span of considering each color.
Example 7
Fig. 1 is the sectional view of expression according to the general configuration of the cathode ray tube of the inventive method manufacturing.In Fig. 1, cathode ray tube 1 comprises panel 2, be configured in the overscan area territory 8 on panel 2 outer surfaces, cover the NGP zone (mainly being silicon dioxide) in overscan area territory 8 for the silica gel form, be configured in the fluorescent material 5 on panel 2 inner surfaces, be formed at the deposit aluminium film 6 on the fluorescent material 5, shadow mask 7 is with sintered glass etc. and the panel 2 pipe awl 3 of welding mutually.
Then the operation that forms overscan area territory 8 and NGP zone 9 is described.At first, the outer surface of the panel 2 of the cathode ray tube 1 made of alkaline cleaner of producing with Henkel-plain boiled water society and crocus (for example cerium oxide) cleaning.Organic dyestuff add a kind of solution (this solution by conductive materials (SnO2+Sb2O3), silester, with example 1 in mixed solvent, water and the acid catalyst of identical component) in the mixed solution that obtained apply equably on the outer surface, form overscan area territory 8 with spinner, in this case, make the cathode ray tube of 14 inches types, the amount of the mixed solution that is coated with is 10ml, the rotating speed of spinner is 100 rev/mins, and the coating time is 1 minute.Then, the cathode ray tube that is obtained is put into stove, make the panel surface be preheating to about 50 ℃; In this state, steam is introduced in the stove, made the panel surface be exposed in the steam about 5 minutes.Then on the panel surface, spray the solution that forms NGP zone usefulness with following component.
Silester 2.5% weight
Ethanol 55% weight
Nitric acid and water 40% weight
Additive 2.5% weight
The cathode ray tube that is obtained is placed in the stove, carries out 30 minutes heat drying under 160 ℃ temperature, to make the overscan area territory 8 with selective light absorption characteristic and the cathode ray tube of NGP zone (being mainly the silicon dioxide of silica gel form) 9.
The cathode ray tube of Huo Deing has 1 * 10 like this
8The sheet resistance of Ω/ and 80% gloss number that records by Japanese industrial standard JIS Z 8741, can not reduce, and the cathode ray tube that is faded than prior art by the caused colour of exterior light (especially ultraviolet ray) lacks owing to erasing panel surface make the coloured dye that gives the selective light absorption characteristic.Therefore, can obtain to have for example yin xian-ray tube of the good characteristic of high-contrast and anti-dazzle property.
Example 8
According to the operation of example 7, on the panel outer surface of cathode ray tube, form the overscan area territory.Subsequently cathode ray tube is put into stove; Panel is preheating to 50 ℃, is exposed in the steam then, and use with example 7 in the same solution in used formation NGP zone spray continuously; At last cathode ray tube heat drying 30 minutes under 160 ℃ of temperature.
The overbrushing layer panel of Huo Deing has identical high-quality in the situation with example 7 like this.
Example 9
Make cathode ray tube stand with example 7 in identical panel surface treatment, thereafter, have to example 7 in the solution spraying used of the formation overscan area territory of similar kind on the panel surface.Identical in follow-up operation and the example 7, thus cathode ray tube made with overscan area territory and NGP zone.
In this case, the overbrushing layer panel that is obtained also has 5 * 10
8The sheet resistance of Ω/ and by 75% measured gloss number of Japanese industrial standard JIS Z 8741 can not make color pigment reduce, and have optical stability.
Comparative example 2
With with example 7 in identical mode form overscan area territory and NGP zone, just these zones are not exposed in the steam.From forming the overscan area territory, comprise that preheating is 10 minutes to the time that forms the NGP zone.
On the overbrushing layer panel that obtains like this, the dyestuff in overscan area territory can slowly be exuded on the outer surface of NGP, and when exerting oneself erasing panel surface with ethanol, the part that dyestuff can occur reduces.In addition, test shows by daylight or UV-induced colour and fades than the fast approximately twice of the sample of example 7-9.
Comparative example 3
Be respectively 2 hours and 24 hours with time interval between the formation NGP zone except forming the overscan area territory, two kinds of cathode ray tubes be with comparative example 2 in identical mode prepare.
The cathode ray tube table in 2 hour time interval shows improvement slightly aspect the dyestuff minimizing, but this improvement is inadequate.The cathode ray tube table in 24 hour time interval shows dyestuff can not reduced, but is to be not suitable for practical use at interval 24 hours the time.
Comparative example 4
With with example 7 in identical mode prepare cathode ray tube, just utilize ultrasonic wetting room temperature to spray contact with steam to change into.Cathode ray tube shows improvement a little at table aspect the dyestuff minimizing, but can not prevent fully that dyestuff from reducing.
Example 10
Fig. 1 is the sectional view after the structure partial of an embodiment of expression cathode ray tube of the present invention excises.In Fig. 1,1 expression cathode ray tube, the outside framework of cathode ray tube is by constituting with the lower part: panel 2, the glass awl 3 of neck part is arranged, hermetic seal the sintered glass 4 of panel 2 and pipe awl 3.5 expression fluorescent materials, 6 expressions are formed at the deposit aluminium film on the fluorescent material 5.7 expression shadow masks, 8 expressions are formed on overscan area territory on panel 2 outer surfaces with method hereinafter described, and 9 expressions are formed on the overscan area territory 8 to cover the NGP zone in overscan area territory 8.Overscan area territory 8 forms with the following step.
At first, clean the outer surface of the panel 2 of cathode ray tube 1 as shown in fig. 1 according to predetermined operation; Then, with this outer surface of solution spin coating that forms the overscan area territory, this solution contains organic dyestuff and has component shown in the top of table 2; Heat drying 30 minutes under 150 ℃ temperature then is to form overscan area territory 8.Solution component except that dyestuff has been shown in the table 3.By the way, the dyestuff title shown in the table 2 is the title described in " dyestuff handbook " (published by ball kind (Maruzen) June 6 nineteen fifty-nine).Each C.I.No. in the table 2 represents the Colour index number described in this this handbook (Color index).
Example 11-12
Become the respective components shown in table 2 and the table 3 except forming the solution of using in the overscan area territory, the overscan area territory 8 in the example 11 and 12 be with example 10 in identical mode form.
Example 13
Overseas except forming double-deck overscan area as the solution that forms the overscan area territory with two kinds of solution of component shown in the table 2, overscan area territory 8 be with example 10 in identical mode form.
Example 14
Overseas except form overscan area with spraying process, overscan area territory 8 be with example 10 in identical mode form.
Example 15
Overscan area territory 8 be with example 10 in identical mode form, then solution spraying with component shown in the table 4 on overscan area territory 8, to form NGP zone 9.
Example 16
Except the overscan area territory forms with spraying process, made the cathode ray tube that has with the identical formation of cathode ray tube of example 15.
Comparative example 5
Except the organic dyestuff of the solution that is used to form the overscan area territory only for the acid rhodamine B, overscan area territory 8 be with example 10 in identical mode form.
Each overbrushing layer panel to above-mentioned preparation carries out measuring such as tone, chemical stability (ChemicalStrength) and light resistance (Optical Strength).Measurement result is shown in the lower part of table 2.
Because (a) the blue look of radiation spectrum B(that penetrates from fluorescent material) and the G(green) between unnecessary Neutral colour C reach (b) radiation spectrum G and R(redness) between the disappearance (see figure 2) of unnecessary Neutral colour M, in table 2, hue table is understood the definition by the given image of each prepared overbrushing layer panel, and uses among the Fig. 3 that is obtained by each overbrushing layer panel spectral transmittance curve 1,2 or 3 to represent.When measuring chemical stability and light resistance, each multilayer panel is immersed in boiling water (chemical stability) or is exposed to (light resistance) under the direct sunlight, then by some hrs (chemical stability) or some day (light resistance) check, indicate that than (the situation I among Fig. 4) time that 20% transmittance deterioration (the situation II among Fig. 4) or table show 50% transmittance deterioration (the situation III among Fig. 4) measures the deterioration condition of spectral transmittance with respect to initial transmission up to each overbrushing layer panel.
Table 3
（SnO2+Sb2O3）
Silester 1.3% weight
Solvent, water and catalyst 97.5% weight
Table 4
Silester 2.5% weight
Alcohol 55% weight
Catalyst and water 40% weight
A small amount of component 2.5% weight
Following situation is very clearly from table 2.
About tone, each overbrushing layer panel of example 10 to 16 is absorbed in the light of M and C scope fully, and demonstrates good optical characteristics.By contrast, the light that the overbrushing layer panel table of comparative example 5 shows the M scope fully absorbs, but is not absorbed in the light of C scope, thereby low in blue color range colorimetric purity.
About chemical stability and light resistance, each multilayer panel of example 10-16 demonstrates high value, and each overbrushing layer panel of example 15-16 demonstrates extra high value.By contrast, the overbrushing layer panel of comparative example 5 demonstrates low slightly chemical stability and lower light resistance.This shows that mixing two or more organic dyestuff of use has for chemical stability and sunproof best cooperation effect, and shows that the existence in NGP zone has contribution greatly to improving chemical stability and light resistance.
As mentioned above, can solve the variety of issue of prior art according to the method for manufacturing cathode ray tube of the present invention, and a kind of cathode ray tube can be provided simply, and this cathode ray tube has wide and stable optical characteristics, high image contrast and anti-dazzle characteristic and avoids by the caused panel of electrostatic induction charged.
In addition, in an embodiment of cathode ray tube of the present invention, optionally absorbed simultaneously from the unnecessary middle color of the spectrum that fluorescent material sent, thereby improved image contrast, improved colorimetric purity, and formed image more clearly.
And, from forming transparent colorful conductive film, want 120 minutes at least in the prior art to forming the required time of anti-dazzle protection film, the method according to this invention then can shorten to below 5 minutes or 5 minutes, and promptly about 1/20 or still less.These a large amount of productions for cathode ray tube are very big advantages.
Claims (19)
1, a kind of cathode ray tube is characterized in that: have to comprise the coating of column region down at least a portion of its panel outer surface:
(A) at least one transparent color conductive region of forming by following component: (a) at least a organic dyestuff, (b) at least a conducting metal oxide of from tin oxide, indium oxide and antimony oxide, selecting, and the silicon dioxide that (c) is mainly the silica gel form
(B) at least one is mainly the anti-dazzle protection zone that silicon dioxide constituted of silica gel form,
This layer anti-dazzle protection zone (B) is formed on the described transparent color of one deck at least conductive region (A).
According to the cathode ray tube of claim 1, it is characterized in that 2, described transparent color conductive region (A) is one deck pantostrat, described anti-dazzle protection layer (B) is formed thereon with the form of dish type that overlaps each other or annular.
According to the cathode ray tube of claim 1, it is characterized in that 3, the described transparent color of one deck at least conductive region (A) is dish type or the annular form that overlaps each other, described one deck anti-dazzle protection zone (B) formed thereon is one deck pantostrat.
According to the cathode ray tube of claim 1, it is characterized in that 4, described transparent color conductive region (A) is dish type or the annular form that overlaps each other, described anti-dazzle protection zone (B) formed thereon is dish type or the annular form that overlaps each other.
According to the cathode ray tube of claim 1, it is characterized in that 5, described transparent color conduction region optionally is absorbed in light and the interior light of 480-500nm wave-length coverage in the 560-600nm wave-length coverage.
According to the cathode ray tube of claim 1, it is characterized in that 6, the described silicon dioxide that is mainly the silica gel form has form of film, and/or is made up of minuteness particle.
According to the cathode ray tube of claim 1, it is characterized in that 7, the particle diameter of described at least a conducting metal oxide is 100nm or below the 100nm.
8, a kind of method of making cathode ray tube is characterized in that, this method may further comprise the steps:
(A) a kind of alcoholic solution that contains following component of coating at least a portion of cathode-ray tube screen face outer surface: (a) at least a organic dyestuff, (b) at least a conducting metal oxide of from tin oxide, indium oxide and antimony oxide, selecting, (c) alkyl silicate, (d) water and (e) acid catalyst
(B) coating contains the alcoholic solution of alkyl silicate on the surface of the panel that was coated with of the surface that is obtained in step (A), and
(C) the not dried overbrushing layer panel that is obtained carried out heat drying in step (B).
9, method according to Claim 8 is characterized in that, described alkyl silicate is a silester.
10, method according to Claim 8 is characterized in that, described acid catalyst is at least a acid of selecting from hydrochloric acid, nitric acid, acetate and sulfuric acid.
11, method according to Claim 8, described alcohol are the mixtures of ethanol and isopropyl alcohol.
12, method according to Claim 8 is characterized in that, described coating is carried out in any mode in spraying, dip-coating and the spin coating.
13, method according to Claim 8 is characterized in that, carries out 5-120 minute heat drying under 80 ° of-250 ℃ of temperature.
14, a kind of method of manufacturing cathode ray tube according to Claim 8 is characterized in that described step (A) and then comprises the lip-deep step that steam is added in the panel that the surface applied that obtained in the step (A) crosses.
According to the method for claim 14, it is characterized in that 15, the temperature of described steam is 30 °-100 ℃.
According to the method for claim 14, it is characterized in that 16, described alkyl silicate is a silester.
According to the method for claim 14, it is characterized in that 17, described acid catalyst is at least a acid of selecting from hydrochloric acid, nitric acid, acetate and sulfuric acid.
According to the method for claim 14, it is characterized in that 18, described alcohol is the mixture of ethanol and isopropyl alcohol.
According to the method for claim 14, it is characterized in that 19, described coating is to carry out with in spraying, dip-coating and the spin coating any.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12111590 | 1990-05-14 | ||
| JP121115/90 | 1990-05-14 | ||
| JP133806/90 | 1990-05-25 | ||
| JP211720/90 | 1990-08-13 | ||
| JP21172090 | 1990-08-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1056602A CN1056602A (en) | 1991-11-27 |
| CN1020223C true CN1020223C (en) | 1993-03-31 |
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ID=26458556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91103125 Expired - Fee Related CN1020223C (en) | 1990-05-14 | 1991-05-13 | Cathode-ray tube and process for producing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1020223C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325176C (en) * | 2001-05-09 | 2007-07-11 | 中华映管股份有限公司 | Method for forming antireflcting and antistatic coating on black display panel of information display |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100265777B1 (en) * | 1993-08-05 | 2000-09-15 | 김순택 | A manufacturing method of anti-reflective layer for screen display device and a screen display device manufactured by the same method |
-
1991
- 1991-05-13 CN CN 91103125 patent/CN1020223C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325176C (en) * | 2001-05-09 | 2007-07-11 | 中华映管股份有限公司 | Method for forming antireflcting and antistatic coating on black display panel of information display |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1056602A (en) | 1991-11-27 |
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