CN1081704A - Additional blue-emitting phosphor and the color cathode ray tube that pigment is arranged - Google Patents

Abstract

The invention provides a kind of additional additional blue-emitting phosphor that pigment arranged that the blue pigments that has fastness and chemical stability and have excellent reflective spectral property arranged and a kind ofly have a color cathode ray tube that on the internal surface of face screen, is formed with the blue light fluorescent layer that contains blue pigments.The present invention also provides the additional CoOZnOSiO that has ₂The additional of class blue pigments has the blue-emitting phosphor of pigment and face to shield the color cathode ray tube that contains the blue light fluorescent layer of this blue pigments particle on the internal surface.

Description

Additional blue-emitting phosphor and the color cathode ray tube that pigment is arranged

The additional blue-emitting phosphor that pigment arranged that the present invention relates to that a kind of fluorescent layer that is suitable as color cathode ray tube etc. uses and a kind ofly have a color cathode ray tube that on the internal surface of its face screen, contains the blue light fluorescent layer of blue pigments.

Contrast gradient for the image that improves color cathode ray tube, fluorescent imaging pipe etc., known and to have adopted the additional method that the fluorescent agent of pigment is arranged, the optical filtering particle that this method system can be absorbed in the external light reflection at window of tube place appends to fluorescent agent surface (USP3,886,394 and USP4,307,320); Or employing tinted shade is as the method for the face screen of cathode tube.

In the method that adopts tinted shade as cathode tube face screen, the transmissivity of glass has reduced, thereby contrast gradient can be relatively easily selected in the scope of a practicality, yet, it not only absorbs outer light but also has increased absorption to this fluorescent layer issued light, thus brightness to reduce be sizable.

Adopting fluorescent agent with pigment to be used as fluorescent layer is a kind ofly not reduce brightness of screen as far as possible and can improve the method for contrast gradient effectively.

Above-mentioned ray filtering material is used for strengthening the luminescent spectrum of fluor sometimes.It is then lower in other wavelength region may to require this ray filtering material to have high transmittance in the emission wavelength zone of fluorescent agent.Utilize this transmission characteristics to absorb, thereby can under bright outer light, improve contrast gradient with the luminous inconsistent light component of fluorescent agent itself.

For the fluorescent agent of blue light-emitting, use about 450mm the i.e. emission peak place of this fluorescent agent that as far as possible little absorption is arranged and be proper at the pigment that other wavelength region may have a big as far as possible absorption.

As this class blue pigments, open in the clear 54-28784 communique the spy and to have proposed ultramarine (3NaAlSiO ₂Na ₂S ₂), Prussian blue (Fe ₄IFe(CN) ₆I ₃NH ₂O), Leyden blue (CoOnAl ₂O ₃), cerulean blue (CoOnSnO ₂), cupric sulfide (CuS) etc.

Yet, from the luminescent spectrum of the fluorescent agent of the present application people's the body colour of discovering common employed Leyden blue and blue light-emitting and inconsistent.The reflectivity of Leyden blue is high especially near 490nm, and this just can't improve contrast gradient effectively.

Also have actual ultramarine of using to compare and has excellent characteristic to a certain extent, but its chemical stability is very low with Leyden blue, thereby in the step that appends to fluorescent agent be coated in the step of cathode tube and COLOR FASTNESS PROBLEM can occur.

For preventing to fade, known and to have adopted the method that ultramarine pigment is wrapped up with silicate compound.With regard to existing the problem that significantly changes takes place when yet it is applied on the cathode tube, thereby the peak in the fluoroscopic emmission spectrum is offset probably because of the electron beam irradiation makes its body colour.

In this case, the present invention attempts to address the above problem, a kind of additional blue-emitting phosphor that pigment is arranged that comprises the fluorescent substance of the blue light-emitting that is added with blue pigments is provided, it has fastness and chemical stability and excellent reflective spectral property, can obtain good blue-light-emitting when therefore being coated on the cathode tube, and a kind of color cathode ray tube that contains the blue light fluorescent layer of above-mentioned blue pigments at the internal surface of its face screen that is provided with is provided.

The invention provides a kind of blue-emitting phosphor with pigment, it comprises a kind of fluorescent agent and a kind of lip-deep blue pigments of fluorescent agent that is attached to this blue light-emitting of blue light-emitting, and described pigment is CoOZnOSiO ₂Class pigment; And provide a kind of internal surface that has at its face screen that comprises to contain the color cathode ray tube of fluorescent layer of the blue light-emitting of blue pigments particle, wherein adopt CoOZnOSiO ₂Class pigment is as this blue pigments particle.

Well-known this CoOZnOSiO ₂Class pigment is mainly as being used for the painted glaze colouring matter of pottery.Yet this raw material is not used alone as pigment etc. usually, and to have only particle diameter usually be that this raw material of 5-10 μ m just can be used as the glaze colouring matter.Therefore it has the fluorescent agent Application for Field of pigment also not to be studied additional at all, because fluorescent agent requires the pigment particles size to be approximately 1 μ m or littler.

Here, CoOZnOSiO ₂Class pigment normally contains the raw material dozens of minutes to tens hour of Co, Zn and Si being not less than burning under 1000 ℃ the temperature, with postcooling and pulverize and obtain.This pigment comprises hopcalite or its combination oxide of these elements, the mixture of cobaltous silicate and zinc silicate or this both sosoloid, with and composition thereof.This xCoOyZnOzSiO ₂The ratio of component of class pigment better is in the scope of 0.05≤x/z≤1.5 and 0.1≤y/z≤2.0, preferably in the scope of 0.2≤x/z≤1.0 and 0.3≤y/z≤1.7.If ratio is outside this scope, tone will change, and this blue pigments just is not suitable for making up with the fluorescent agent of blue light-emitting like this.Combination oxide comprises hopcalite or its composite oxides of element separately, cobaltous silicate and zinc silicate mixture or its sosoloid, and their mixture.

If desired, when firing above-mentioned pigment, can add various fusing assistants and other element.More specifically, be to add Li, Na, K, Ca, Mg, Ba, Fe, Ni, Cu, Mn, Ti, V, Al, Sn, Sb, Cr, Pr etc.These compositions can be no more than 10% weight adding.If the total amount that adds surpasses this scope, this blue pigments just can't obtain needed tone.

And the synthetic method of blue pigments has no particular limits.For example can synthesize by following method.

(1) dry type mixed sintering method

This method is by contain the raw material of Co, Zn and Si with a predetermined ratio preparation, by ball mill they are mixed, under about 1000 ℃-1300 ℃ temperature, fire mixture dozens of minutes to tens hour, with postcooling and pulverize, obtain this pigment after choosing divides.

(2) coprecipitation method

This method is to make cobalt and zinc as the oxyhydroxide coprecipitation by adding the alkaline water dissolubility to the aqueous solution that contains cobalt and zinc, by organic solvent with the water displacement after, with hydrolysis Si oxide is deposited on the precipitation face, fire subsequently and obtain this pigment.

Here conduct is used for the cobalt of obtained aqueous solution and the compound of zinc can adopt oxide compound, fluorochemical, iodide, bromide, vitriol, nitrate etc.Organic solvent as replacing water can adopt silicic acid alkoxide etc. as the silicon raw material.Firing temperature is in 700-1000 ℃ scope in the air.

(3) co-precipitation/dry type mixed sintering method

This method is by add the organic compound as precipitation agent to the aqueous solution that contains cobalt and zinc, this compound can be dissolved in the water and with cobalt and zinc reaction generation and be insoluble in water or water-fast material, with cobalt and zinc coprecipitation, then dry, mix with Si oxide and to fire again and obtain this pigment.

The aqueous solution that contains cobalt and zinc that adopted is similar to and is adopted in the above-mentioned coprecipitation method.As precipitation agent better is that employing itself is dissolvable in water water and can generates the organic compound that be insoluble in water or water-fast material with the reaction of cobalt and zinc, oxalic acid for example, tartrate.As Si oxide better is to adopt to have good reactive behavior, and specific surface area is 100m ²The anhydride of the ultramicron that/g is above.Firing temperature is usually in 800-1100 ℃ scope.Especially above-mentioned coprecipitation method and co-precipitation/dry type mixed sintering method is novel manufacture method, littler by these methods ratios by the particle diameter of traditional resulting pigment of dry type mixed sintering method, additional pigment as the fluorescent agent use, all more suitable at aspects such as color, sticking power, and can easily make.

Can be used on the coloured light fluorescent agent that turns blue of the present invention and comprise the fluorescent agent of those major portions in the 380-500nm scope with emmission spectrum, silver activates zinc sulfate class fluorescent agent [ZnS:Ag more specifically, X(X is halogen or Al), ZnS:Ag, M, X, (M is a gallium, indiums etc., X are halogen or Al)], Y ₂SiO ₅: Ce, Ca ₂B ₅O ₉Cl:Eu, (Ba _xMg _1-x) OnAl ₂O ₃: Eu(0≤x≤1,7≤n≤8), SrSi ₃O ₈Cl ₄: Eu, CaWO ₄, CaWO ₄: Pb, BaFCl:Eu, Gd ₂O ₂S:Tb, ZnS:Zn etc.

The additional content that is added to the blue pigments of blue light-emitting fluorescent agent better is in the scope of 0.3 to 30 weight %.If this additional content is lower than lower limit, its filter effect will be too little, surpasses the upper limit and work as it, and luminosity is just abundant inadequately.

The inventor has studied variously to have with the consistent body colour of emmission spectrum of blue light-emitting fluorescent agent, is subjected to the various pigment that long electron beam irradiation damages hardly or fades as the fluorescent layer of cathode tube the time in a vacuum.They find above-mentioned CoOZnOSiO as a result ₂The class blue pigments can satisfy above-mentioned requirements.They also find have the face of the blue light-emitting fluorescent agent coating of blue pigments to shield by adopting by additional, or adopt the face of the fluorescent layer that has the blue light-emitting that contains the blue pigments particle that between the fluorescent layer of face screen and blue light-emitting, is coated with coat of colo(u)r to shield, can be when keeping brightness, though obtain the window of tube of high-contrast and provide a kind of under very bright outer light also apparent color cathode ray tube.

Among the present invention by taking above-mentioned composition, and can with have with the corresponding to specular reflectance excluded of emmission spectrum of the fluorescent agent of blue light-emitting and aspect fastness and chemical stability all excellent blue pigments append in the fluorescent agent of blue light-emitting.A kind of fluorescent agent of fine blue light-emitting can also be provided, and rotten or color shift or can not take place when being applied to cathode tube in it in additional step or coating step.And then, between the fluorescent layer of face screen and blue light-emitting, be provided with above-mentioned blue pigment layer, window of tube just can obtain high-contrast when keeping brightness, thereby a kind of still color cathode ray tube of apparent screen that has under very bright illumination just might be provided.

Fig. 1 illustrates Leyden blue pigment and CoOZnOSiO ₂The figure of the diffuse reflection spectrum of class pigment.

Fig. 2 is the fluorescent agent ZnS:Ag that typical blue light-emitting is shown, the figure of the emmission spectrum of Cl fluorescent agent.

Fig. 3 shines ultramarine, Leyden blue pigment or CoOZnOSiO with the X of CIE mode, Y value representation at electron beam ₂The figure of the color shift during class pigment.

Fig. 4 represents to contain respectively Leyden blue pigment or CoOZnOSiO ₂Diffuse at 490nm and the 450nm place ratio R of spectrum peak of the fluorescent agent of the blue light-emitting of class pigment ₄₉₀/ R ₄₅₀Figure.

Fig. 5 and Fig. 6 represent to contain respectively Leyden blue pigment or CoOZnOSiO ₂The specular reflectance excluded distribution plan of the fluorescent agent of the blue light-emitting of class pigment.

Fig. 7 is the median size of expression blue pigments and the graph of a relation of sticking power.

Fig. 8 is the part cross-sectional side elevational view of the color cathode ray tube of the specific embodiment of the invention.

Fig. 9 is the amplification sectional view of the window of tube major portion of Fig. 8.

Fig. 1 is comparison xCoOyZnOzSiO₂The figure of the diffuse reflection spectrum of class pigment (x=0.36, y=0.6, and z=1.0) and cobalt aluminate pigment. Fig. 2 then is the fluorescer ZnS:Ag that typical blue light-emitting is shown, the utilizing emitted light spectrogram of Cl fluorophor.

From the comparison between Fig. 1 and Fig. 2, obviously with respect to cobalt aluminate pigment xCoOZnOSiO₂The diffuse reflectance of class pigment is that body colour is mutually more consistent with luminescent spectrum and the pigment of fluorescer. And cobalt aluminate pigment has a characteristic peak at about 490nm place, and xCoOyZnOzSiO₂Class pigment does not then have this characteristic peak, thus it to compare with cobalt aluminate pigment in the optical filtering effect at 480 to 520nm places be excellent.

Fig. 3 demonstrates deterioration when the electron beam irradiation by X, the Y value of CIE mode, is about to 20KV, 30 μ A/cm²The electron beam irradiation of intensity is being coated with xCoOyZnOzSiO₂The change of metallic plate body colour during upper 30 minute of class pigment, cobalt aluminate pigment or ultramarine. Fig. 3 shows the order by ultramarine and cobalt aluminate pigment clearly, and body colour takes place to change greatly, and xCoOyZnOzSiO₂Class pigment does not almost change, and this just shows xCoOyZnOzSiO aspect fastness and chemical stability₂Fabulous. This means when being applied to cathode-ray tube etc., even use for a long time body colour and luminous pigment also can not change, is extremely useful in practical application like this.

If particularly consider the caused deterioration of excitation energy by electron beam etc., have fluorescer, Y by the blue light-emitting with pigment of the present invention₂O ₂S:Eu or be attached with the Y of iron oxide red red pigment₂O ₃: the fluorescer that Eu glows and ZnS:Cu, the fluorescer of Al green light or be attached with TiO₂Each blueness, redness and the green fluorescence coating that the fluorescer combination of the green light of ZnOCoONiO class viridine green obtains just can demonstrate very stable contrast and luminous color as the color cathode ray tube of fluorescence coating, thereby is useful.

The present application people has studied CoOZnOSiO₂The average grain diameter of class blue pigment and the relation between the adhesive force, and found relation as shown in Figure 7. Adhesive force is Vibration and mixing are added with the fluorescer of pigment in the water that is added with 0.1% surfactant, make it leave standstill 2 hours, measure the transmissivity of supernatant liquor at the 600nm place. If numerical value is littler, pigment is peeled off in water, thus transmissivity will to reduce this adhesive force that just shows pigment low. Fig. 7 clearly illustrates that if the average grain diameter of this face grain surpasses 0.5 μ m, adhesive force is just little, thereby preferably is no more than 0.5 μ m from the average particle diameter of the viewpoint of practical application.

Also have, consider the relation of the color development of special and this class pigment, average grain diameter is preferably in the scope of 0.1-0.45 μ m.

Fig. 8 is that the part of color cathode ray tube of the present invention is dissectd side view. Fig. 9 is the amplification sectional view of the fluorescent screen major part of Fig. 8. The formation of panel paint layer is realized by the lithoprinting technology as the formation of fluorescence coating. At first, with first graining paste, for example a kind of by viridine green with such as the thin pulp of the compositions of mixtures of ammonium dichromate (after this representing with ADC) and polyvinyl alcohol (after this representing with PVA) light sensitivity bond, be coated on the inner surface of the face screen 1 that before has been formed with black matrix" 2 thereon, then the dry rete that forms. This rete exposes by shadow mask, and video picture makes viridine green rete 3 form predetermined pattern. Subsequently, second graining paste for example a kind of blue pigment slurry by blue pigment and the compositions of mixtures of light sensitivity bond make blue pigment rete 4 form predetermined pattern on the different position of viridine green rete 3 in the above with above-mentioned identical method. Next, the 3rd graining paste is a kind of red pigment slurry for example, makes red pigment rete 5 form predetermined pattern on the other position of viridine green rete 3 and blue pigment rete 4 in the above with above-mentioned identical method.

Green fluorescer, blue-fluorescence agent and red fluorescence agent are coated in respectively on the pigment rete of color separately to form green fluorescer pixel 6, blue-fluorescence agent pixel 7 and red fluorescence agent pixel 8 by the lithoprinting technology then. AM aluminum metallization plasma membrane layer is metal-backed to form one deck thereon again, has so far just finished the fluorescent screen on the face screen 1. The screen 10 of this face screen 1 is not sealed by funnel 11, and just forms color cathode ray tube after loading onto electron gun 12.

Embodiment 1

With 1.7 parts of cobalt oxides, 2.6 parts of zinc oxide and 5.8 parts of silicon oxide mix with dry type, fire 2 hours at 1300 ℃ in air, pulverize sorting subsequently and obtain the xCoOyZnOzSiO that median size is 1.7 μ m ₂Class pigment (x=0.36, y=0.6 and z=1.0).

The fluorescent agent that 100 parts of distilled water is added to 100 parts of silver activation zinc sulphide blue light-emittings obtains thin pulp, again with 1 part of above-mentioned xCoOyZnOzSiO ₂Class pigment (x=0.36, y=0.6 and z=1.0) is added in this thin pulp.The aqueous solution of gum arabic that adds 0.36 part of gelatin and 0.3 part when being heated to 45 ° again is as wedding agent, and with acetic acid pH adjusted to 4.1.Allow mixture be cooled to room temperature, add 7.5 part of 50% glutaraldehyde water solution then wedding agent is solidified.

Also have,, can make the fluorescent agent that is added with pigment of embodiment with same procedure except the addition with pigment makes into 3 parts, 5 parts and 7 parts.

And then, for relatively,, add the additional fluorescent agent that pigment is arranged that can obtain Comparative Examples by the same procedure of the foregoing description except replacing the top pigment by Leyden blue pigment with 1 part, 3 parts, 5 parts and 7 parts.

Fig. 4 measures the fluorescent agent of the foregoing description and 8 kinds of additional pigment of this two class of Comparative Examples at the resulting figure of the specular reflectance excluded of 490nm and 450nm, and then maps as X-coordinate as the additional content of ordinate zou pigment with (reflectivity of 490nm)/(reflectivity of 450nm).Fig. 4 clearly illustrates that the fluorescent agent that has added pigment of embodiment is compared with Comparative Examples, has less value, thereby has bigger filter effect.

Fig. 5 is fluorescent agent (curve specular reflectance excluded distribution comparison diagram a) that is added with 3 parts of pigment in the foregoing description in the additional fluorescent agent (curve b) that 7 parts of pigment are arranged and the above-mentioned Comparative Examples.Fig. 5 clearly illustrates that the fluorescent agent of Comparative Examples shows the peak at about 490nm place, and the fluorescent agent of embodiment does not then have such peak and can conform to the luminescent spectrum of fluorescent agent preferably.

Embodiment 2

The xCoOyZnOzSiO that has the 5 weight % that make by dry type mixed sintering method by employing ₂Combination oxide (x=1.0, y=1.0 and z=1.0) blue pigments, the PVA(polymerization degree 2400 of 2 weight %, saponification degree 88%), the sodium dichromate 99 (Kanto Kagaku K. K.'s system) of 0.15 weight %, the pigment slurry that the tensio-active agent of 0.03 weight % and remaining water are formed is that the blue pigments rete of 1 μ m is formed on the internal surface of face screen by photolithographic methods with mean thickness.

Subsequently, by adopting ZnS:Ag, Cl is formed on blue-fluorescence agent pixel on the blue pigments rete as the fluorescent agent of the blue light-emitting method with routine.

For relatively, replace above-mentioned blue pigments by applying Leyden blue or ultramarine, coating thickness is identical with the foregoing description, forms window of tube (Comparative Examples 1 and 2) with method same as the previously described embodiments.

Except not using the pigment to form window of tube (Comparative Examples 3) with top identical method.

Brightness and contrast's comparison

As shown in table 1 to the result that each fluoroscopic brightness and contrast of the foregoing description and Comparative Examples is measured.The value of contrast gradient is the ratio that is expressed as when by outer photoirradiated surface screen surfaces in the brightness of the brightness of light (part that emits white light when loading onto) and shade (when loading onto not luminous component) in addition.

Table 1 clearly illustrates that the window of tube of embodiment is compared with two Comparative Examples, and the minimizing of white brightness is less, has kept higher contrast ratio.

Table 1

Pigment white colour brightness contrast gradient

Embodiment 2 CoZn-Si are combination oxide 95 125

Comparative Examples 1 Leyden blue 86 115

Comparative Examples 2 ultramarines 89 125

Comparative Examples 3 no pigment 100 100

Embodiment 3

4.7 parts of cobalt chloride (hexahydrate) and 5.5 parts of zinc chloride are dissolved in 100 parts of deionized waters.Under agitation progressively add the 1N aqueous sodium hydroxide solution pH is adjusted to 9.Allow mixture leave standstill, remove supernatant liquid, add the ethanol of equal volume.Make mixture leave standstill again, change supernatant liquid with ethanol.Again to the ammoniacal liquor that wherein adds 24 part 28%.Under agitation 20 parts of tetraethoxysilanes are dissolved in 20 parts of alcoholic acid solution then and add, with this mixture heating up to 40 ℃ and kept 2 hours.After this reaction was finished, the solid phase prod that will obtain through centrifugation, and was fired at 800 ℃ and to be obtained the xCoOyZnOzSiO that median size is 0.3 μ m in 2 hours removing ethanol through air-dry ₂Pigment (x=0.3, y=0.6 and z=1.0).

Then, 100 parts of distilled water are added in the fluorescent agent of 100 parts of silver activation zinc sulphide blue light-emittings and make thin pulp.Add 7 parts of above-mentioned blue pigmentss again, when being heated to 45 ℃, add 0.36 part of gelatin and 0.3 part of Arabic gum aqueous solution, pH is adjusted to 4.1, allow mixture be cooled to room temperature with acetic acid as wedding agent.Then, adding 7.5 part 50% glutaraldehyde water solution again solidifies wedding agent.

The comparison of filter effect

Measure the additional fluorescent agent specular reflectance excluded that pigment is arranged that obtains among the embodiment 3, the result is shown in curve c among Fig. 5.Curve b among fluorescent agent among the additional embodiment 3 that tiny pigment particles arranged and embodiment 1(Fig. 5) though to compare the additional content of pigment be identical in these embodiments, near 600nm, demonstrates the filter effect of lower reflectivity and excellence.

Embodiment 4

The preparation embodiment of blue pigments

32 parts of cobalt oxides (hexahydrate) and 22.3 parts of zinc chloride are dissolved in 500 parts of deionized waters.In addition 40 parts of oxalic acids (dihydrate) are dissolved in 500 parts of deionized waters.Under agitation the oxalic acid aqueous solution is joined in the metal salt solution.Continue to stir 15 minutes, make this mixture leave standstill 1 hour, remove supernatant liquid, then dry down at 90 ℃.Be 200m with this product and 9.67 parts of specific surface areas after the drying ²The Si oxide dry type of/g is mixed, and fires this mixture 1 hour at 1000 ℃, grinds and obtains the xCoOyZnOzSiO that median size is 0.14 μ m ₂Class blue pigments (x=0.8, y=1.0 and z=1.0).

Add the preparation embodiment of the fluorescent agent of the blue light-emitting that blue pigments is arranged

100 parts of distilled water are added in the fluorescent agent of 100 parts of silver activation zinc sulphide blue light-emittings to make thin pulp.Add 3 parts of above-mentioned blue pigmentss again, when being heated to 45 ℃, add 0.36 part of gelatin and 0.3 part of Arabic gum aqueous solution as wedding agent.With acetic acid pH is adjusted to 4.1 and allow mixture be cooled to room temperature.Add 7.5 part of 50% glutaraldehyde water solution then so that wedding agent solidifies.

Embodiment 5

Dry type is mixed 60 parts of cobalt oxides, 103 parts of zinc oxide and 64 parts of silicon oxide, fires this mixture 2 hours in air and pulverized at 1300 ℃ then to obtain the xCoOyZnOzSiO that median size is 0.64 μ m ₂Pigment (x=0.8, y=1.3 and z=1.0).

This blue pigments being added to silver activation zinc sulphide under the condition identical with embodiment 4 turns blue in the coloured light fluorescent agent.

The comparison of filter effect

Specular reflectance excluded to the fluorescent agent that is added with pigment that obtains among embodiment 4 and the embodiment 5 is measured, and the result is illustrated by a among Fig. 6 and b.Although the pigment additional content is identical in these embodiments, added fluorescent agent than the embodiment of the pigment of small-particle, near 600nm, demonstrate lower reflectivity and more excellent filter effect.

Claims (10)

1, a kind of additional blue-emitting phosphor that pigment is arranged, the blue pigments that it is characterized in that comprising the fluorescent agent of blue light-emitting and append to the coloured light fluorescent agent surface of turning blue, described blue pigments is a CoOZnOSiO class pigment.

2, the additional blue-emitting phosphor that pigment is arranged as claimed in claim 1 is characterized in that this blue pigments is by chemical formula xCoOyZnOzSiO ₂Represent that this ratio of components is in the scope of 0.05≤x/z≤1.5 and 0.1≤y/z≤2.0.

3, the additional blue-emitting phosphor that pigment is arranged as claimed in claim 1 is characterized in that the median size of this blue pigments is no more than 0.5 micron.

4, the additional blue-emitting phosphor that pigment is arranged as claimed in claim 1 is characterized in that blue-emitting phosphor is silver activation zinc sulphide class fluorescent agent, Y ₂SiO ₅: Ce, Ca ₂B ₅O ₉Cl:Eu, (Ba _xMg _1-x) OnAl ₂O ₃: Eu(0≤x≤1,7≤n≤8), SrSi ₃O ₈Cl ₄: Eu, CaWO ₄, CaWO ₄: Pb, BaFCl:Eu, Gd ₂O ₂At least a among S:Tb and the ZnS:Zn.

5, the additional blue-emitting phosphor that pigment is arranged as claimed in claim 1, it is characterized in that blue pigments is by add the oxyhydroxide coprecipitation that alkaline aqueous solution makes cobalt and zinc in the aqueous solution that contains cobalt and zinc, and by the organic solvent replacing water, by hydrolysis silicon oxide is deposited on the sedimentary surface, the CoOZnOSiO that obtains in fire ₂The class blue pigments.

6, the additional blue-emitting phosphor that pigment is arranged as claimed in claim 1, it is characterized in that blue pigments is by add can be dissolved in water and forming the organic compound of indissoluble or water-fast material with cobalt and zinc as precipitation agent to the aqueous solution that contains cobalt and zinc, make cobalt and zinc coprecipitation, then dry, the CoOZnOSiO that obtains with the silicon oxide mixed sintering ₂The class blue pigments.

7, a kind of color cathode ray tube is characterized in that being included in the face screen that has blue light fluorescent layer, ruddiness fluorescent layer and green glow fluorescent layer on its internal surface, and wherein the blue light fluorescent layer contains CoOZnOSiO ₂Class blue pigments particle.

8, color cathode ray tube as claimed in claim 7, it is characterized in that the blue light fluorescent layer contains silver activation zinc sulphide fluorescent agent, the ruddiness fluorescent layer contains europium activation oxygen yttrium sulfide or europium active oxidation yttrium fluorescent agent, and the green glow fluorescent layer contains work in copperization and silver activation zinc sulphide fluorescent agent.

9, color cathode ray tube as claimed in claim 7 is characterized in that the ruddiness fluorescent layer contains the red iron oxide red pigment.

10, color cathode ray tube as claimed in claim 7 is characterized in that the green glow fluorescent layer contains TiO ₂ZnOCoONiO class veridian.

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