CN1037188C

CN1037188C - Pigment-attached blue-emitting phosphor and color cathode-ray tube

Info

Publication number: CN1037188C
Application number: CN92109052A
Authority: CN
Inventors: 水上友人; 舩山地人; 小栗康生
Original assignee: Kasei Optonix Ltd
Current assignee: Kasei Optonix Ltd
Priority date: 1992-07-31
Filing date: 1992-07-31
Publication date: 1998-01-28
Anticipated expiration: 2007-07-31
Also published as: CN1081704A

Abstract

The present invention provides a blue light fluorescent agent added with blue pigment with harm-resistant degree, chemical stability and excellent reflection spectrum characteristics and a colored cathode ray tube forming a blue fluorescent layer containing blue pigment on the inner surface of a surface screen. The present invention also provides a blue light fluorescent agent added with CoO. ZnO. SiO2 blue pigment, and a colored cathode ray tube containing the blue light fluorescent layer of blue pigment particles on the inner surface of the surface screen.

Description

The additional blue-emitting phosphor 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 the fluorescent agent surface, and (USP 3,886,394 and USP 4,307,320); 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 450nm 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, more specifically silver activation zinc sulfate class fluorescent agent [ZnS:Ag, X (X is halogen or Al), ZnS:Ag with emmission spectrum, 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 xCoOyZnOzSiO₂Class pigment (x=0.36, y=0.6 and Z=1.0) and the figure of the diffuse reflection spectrum of cobalt aluminate pigment. Fig. 2 illustrates typically to turn blue The fluorescer ZnS:Ag of light, 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 luminescent spectrum and the pigment of body colour and fluorescer Mutually more consistent. And cobalt aluminate pigment has a characteristic peak at about 490nm place, and XCoOyZnOzSiO₂Class pigment does not then have this characteristic peak, thus it 480 to It is excellent that the filter effect at 520nm place is compared with cobalt aluminate pigment.

Fig. 3 demonstrates deterioration when the electron beam irradiation, i.e. 20KV, 30 μ A/cm by X, the Y value of CIE mode²The 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 Become, 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 Changing, 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 TiO₂The green light of ZnOCoONiO class viridine green Each blueness, redness and green fluorescence layer that the fluorescer combination obtains are as fluoroscopic colour Cathode-ray tube just can demonstrate very stable contrast and luminous color, thereby is to have With.

Ask the inventor to study CoOZnOSiO in this₂The average particle of class blue pigment Relation between footpath and the adhesive force, and found relation as shown in Figure 7. Adhesive force is Vibration and mixing are added with the fluorescer of pigment, order in the water that is added with 0.1% surfactant It left standstill 2 hours, measured the transmissivity of supernatant liquor at the 600nm place. If numerical value Little, pigment is peeled off in water, thereby transmissivity will reduce the adhesive force that this just shows pigment Low. Fig. 7 clearly illustrates that, if the average grain diameter of this face grain surpasses 0.5 μ m, adheres to Power is just little, thereby preferably is no more than from the average particle diameter of the viewpoint of practical application 0.5 μ m.

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

Fig. 8 is the part cross-sectional side elevational view of color cathode ray tube of the present invention. Fig. 9 is figure The amplification sectional view of 8 fluorescent screen major part. The screen and the formation of paint layer resembles fluorescence The formation of layer is the same to be realized by photolithographic techniques. At first, with first graining paste, example As a kind of by viridine green with such as ammonium dichromate (after this representing with ADC) and polyvinyl alcohol The thin pulp of the compositions of mixtures of (after this representing with PVA) light sensitivity bond applies formerly Before be formed with on the inner surface of face screen 1 of black matrix" 2 dry formation then thereon Rete. This rete exposes by shadow mask, and it is predetermined that video picture forms viridine green rete 3 Pattern. Subsequently, second graining paste a kind of mixed by blue pigment and light sensitivity bond for example Viridine green rete 3 is not in the above with above-mentioned identical method for the blue pigment slurry that compound forms Make blue pigment rete 4 form predetermined pattern on the position together. Next, the 3rd face Slip is a kind of red pigment slurry for example, with above-mentioned identical method viridine green rete in the above 3 and the other position of blue pigment rete 4 on that red pigment rete 5 is formed is predetermined Pattern.

Then by photolithographic techniques that green fluorescence agent, blue-fluorescence agent and redness is glimmering Photo etching be coated in respectively on the pigment rete of color separately with form green fluorescence agent pixel 6, Blue-fluorescence agent pixel 7 and red fluorescence agent pixel 8. Again thereon AM aluminum metallization plasma membrane layer with Form the layer of metal backing, so far just finished the fluorescent screen on the face screen 1. This face does not shield 1 Screen 10 by funnel 11 sealing, and load onto and just form color cathode behind the electron gun 12 and penetrate Spool.

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=O.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 of the 2 weight % (polymerization degree 2400, 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.Fluorescent agent among the additional embodiment 3 that tiny pigment particles arranged though to compare the additional content of pigment be identical in these embodiments, demonstrates the filter effect of lower reflectivity and excellence with embodiment 1 (the curve b among Fig. 5) near 600nm.

The preparation embodiment of embodiment 4 blue pigmentss

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

1. the additional blue-emitting phosphor that pigment is arranged is characterized in that, comprises the fluorescent agent of blue light-emitting and appends to the blue pigments on this blue-emitting phosphor surface with the consumption of 0.3-30wt%, and described blue pigments has chemical formula: xCoOyZnOzSiO ₂, wherein the relative consumption of the oxide component of this pigment is in 0.05≤x/z≤1.5 and 0.1≤y/z≤2.0 scopes, and described blue-emitting phosphor is silver activation zinc sulphide 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.

2. the additional blue-emitting phosphor that pigment is arranged as claimed in claim 1 is characterized in that described blue pigments obtains through following steps:

Add alkaline aqueous solution to the aqueous solution that contains cobalt and zinc, make cobalt and zinc as the oxyhydroxide coprecipitation,

With the water in the organic solvent displacement mixing solutions, and add and can make the sedimentary silicon raw material of Si oxide by its hydrolytic action,

By hydrolytic action Si oxide is deposited on the sedimentary hydroxide surfaces,

In air, fire the throw out that obtains with 700 °-1000 ℃ temperature.

3. the additional blue-emitting phosphor that pigment is arranged as claimed in claim 1 is characterized in that described blue pigments obtains through following steps:

Add as precipitation agent, can be dissolved in water and react the organic compound that forms indissoluble or water-fast material to the aqueous solution that contains cobalt and zinc with cobalt and zinc,

Make the sedimentable matter drying that obtains,

Make through the exsiccant material and mix with Si oxide,

In air, fire the mixture that obtains with 800 °-1100 ℃ temperature.

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