CN1020743C - Luminous compositions and process for their prepn. and fluorescent lamp using the compositions - Google Patents
Luminous compositions and process for their prepn. and fluorescent lamp using the compositions Download PDFInfo
- Publication number
- CN1020743C CN1020743C CN 86108231 CN86108231A CN1020743C CN 1020743 C CN1020743 C CN 1020743C CN 86108231 CN86108231 CN 86108231 CN 86108231 A CN86108231 A CN 86108231A CN 1020743 C CN1020743 C CN 1020743C
- Authority
- CN
- China
- Prior art keywords
- fluor
- luminous
- mentioned
- earth metal
- luminous compositions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The present invention relates to a luminescent composition which is obtained by granules with fluorophore or fluorophore material and alkaline earth metal sulfate fused together, the manufacturing method of the same and the fluorescent lamp using the same.
Description
The present invention relates to the luminescent lamp of luminous compositions and manufacture method thereof and this constituent of use.Though more particularly to relate to be the luminous compositions be made up of the vitriol of twinkler and alkaline-earth metal, be to contain this non-luminophore in a large number but still can keep high brightness and the manufacture method of the luminous compositions that price is very cheap, this constituent and the luminescent lamp of this luminous compositions as fluorescent screen again.
Because fluor has usually and can be transformed into this property of visible light to excitation energy invisible to the human eye, thus it to compare with simple chemical material be the high price article.Especially in recent years, in order to satisfy various characteristics, develop into its raw material at present and adopted rare earth element and precious metal element in a large number, thereby be subjected to the various restrictions that cause because of price in the use, often can not use such problem thereby produced optimal fluor for its purpose.So people wish that very the valency of this class fluor can step-down.
On the other hand, the technology of relevant this respect is as the technology approaching with the present invention, for example No. 603326 communique of English Patent arranged, wherein be logged into, in luminescent lamp, just can reduce the usage quantity of luminophore by the material that between supporting mass and fluor, sandwiches good ultraviolet line reflection rate.In addition, improvement as this technology, in No. 4069441 communique of United States Patent (USP), disclosed a kind of gas discharge lamp, its structure is, the film that mixture constituted that is mixed the back gained by little white mass of ultraviolet-absorbings such as barium sulfate, Jiao's property calcium phosphate, magnesium oxide and fluor is arranged on the Glass tubing side, stacked thereon then only by the film that fluor constituted, and make white mass in the film that constitutes by said mixture progressively become big towards the Glass tubing side to the ratio of fluor.In addition, the spy that also has as correlation technique opens clear 57-128452 communique.Similarly, other is according to separately special purpose (X ray is as the conversion window of tube), fluor and white pigment merely in addition the blended mixture in communiques such as No. 4039840 communiques of United States Patent (USP), the public clear 56-5478 communique of spy and the clear 55-146447 of Te Kai number, obtained announcement.
In addition, the vitriol of the alkaline-earth metal that disclosed of for example special again public clear 54-37069 communique, special public clear 57-50832 communique is that fluor (promptly making the fluor of parent with the vitriol of alkaline-earth metal) is also known.These fluor contain as the lead of activator and divalent europium, and it can demonstrate ultraviolet or blue luminous for excitation energy.
The mixture of above-mentioned light-emitting fluophor and this white mass, as considering from practical level, then the sinking of its luminosity is very big, for being reduced, this brightness reduces, and in order to produce other effect, must require to take to form the complicated means of special layers structure etc. as above-mentioned each patent gazette is put down in writing, its usage quantity also often is limited in below percentum (weight) in addition.
As mentioned above, all prior aries all fail to accomplish can reduce significantly the price of these luminophores under the brightness that reduces luminophore hardly, and therefore, this fluorescent substance can appear in people's strong request.
The objective of the invention is to provide a kind of reduce hardly for the brightness of excitation energy, be more in surprise even can improve its brightness and can significantly reduce the luminophore of the price of luminophore.
The present inventor in order to achieve the above object, molectron to cheap non-luminescent material and fluor has at high price carried out all research, found that, in case after fluor mixed with the vitriol of alkaline-earth metal and burning till, just can obtain to meet the luminophore of above-mentioned purpose, thereby just finish the present invention.
The present invention relates to contain the vitriol fusion adhesion of handlebar fluor and alkaline-earth metal and the luminous compositions of the particle that forms.
In addition, the present invention relates to the manufacture method of luminous compositions, it is characterized in that burning till under the common state that exists of the vitriol of fluor or phosphor raw material and alkaline-earth metal.
Moreover, the invention still further relates to a kind of luminescent lamp, it is characterized in that in fluorescent screen, containing the luminous compositions that comprises a kind of particle, said particle is to adhere by the vitriol fusion of fluor alkaline-earth metal to form.
Fig. 1 is illustrated in the luminous compositions of the present invention, relative luminosity when the ratio of components of fluor and the vitriol of alkaline-earth metal is changed under ultraviolet ray excited and the relation between the materials cost reduced rate, curve 1 and 2 is a luminous compositions of the present invention, and curve 3 is the mixture of prior art.Relation between the illuminant colour (x value) that Fig. 2 has shown luminous compositions beyond the fluor under ultraviolet ray excited, luminous compositions of the present invention, the present invention and mixture etc. and the relative luminosity.Fig. 3 shown firing temperature when making luminous compositions of the present invention (℃) with relative luminosity (%) between relation.Fig. 4-a is the electron micrograph figure that shows the particle structure of mixture, and Fig. 4-b and Fig. 4-c are the electron micrograph figure that has shown the particle structure of luminous compositions of the present invention respectively.Similarly Fig. 5-a and Fig. 5-b and Fig. 5-c also are the electron micrograph figure that has shown the particle structure of luminous compositions of the present invention respectively.Fig. 6-a and Fig. 6-b are the figure that has shown the X ray diffraction picture of luminous compositions of the present invention respectively.
Below, with the present invention will be described in more detail.
Luminous compositions of the present invention as an example, is (to call method for making 1 in the following text) made as described below. At first, fluorophor is fully mixed with the sulfate of alkaline-earth metal, then under arbitrary temperature of 550～1600 ℃ scope, this mixture is advanced to burn till.
Employed fluorophor in the invention described above can use existing Any in the known fluorophor, but consider from the gas medium that burns till etc., in fact main or use the fluorophor of the oxide series that in meta-element, contains the oxygen such as oxide, oxysulfide, vanadate, silicate, phosphate, aluminate, borate. That is to say, be suitable for the fluorophor that burns till in gas medium, neutral gas medium and the week reduction gas medium at oxygen. In addition, do further to analyze from the viewpoint of practicality, from the reduction effect of fee of material, be applicable to and contain rare earth element and at least a fluorophor of precious metal element that particularly contain in a large number the fluorophor of these elements, this effect is more big. For example, if the present invention be applicable to contain a large amount of practical lamps with fluorophor in its price the highest and be that (composition formula is Ln as the rare-earth oxide fluorophor of activator for the europium of oxide phosphor2O
3: the Eu fluorophor, but Ln is at least a among Y, Gd, La, the Lu), this effect will be very big so. In addition, the sulfate of the said alkaline-earth metal of the present invention is the sulfate of at least a element in barium (Ba), strontium (Sr), calcium (Ca), the magnesium (Mg), as its representational example barium sulfate (BaSO is arranged4), strontium sulfate (S-SO4), calcium sulfate (CaSO4) etc. The sulfate of these alkaline-earth metals, usually with adopt earlier sieve that the aggegation piece is unclamped before fluorophor mixes, sieve out granule, and then the time exercise and use. In addition, the two mixing can utilize mortar and grinder etc. to carry out fully, and dry type and wet type all can.
These mixtures are dropped into heatproof container, under said temperature, burn till, this burning till normally under the temperature below the fusing point of the sulfate of employed fluorophor and employed alkaline-earth metal carried out, and firing time at this moment is dozens of minutes to several hours scope. Although the gas medium when burning till is the gas medium that burns till when using common employed manufacturing fluorophor, also require to possess the condition that the sulfate that makes alkaline-earth metal is difficult to change in letting alone. Above-mentioned firing temperature is preferably 800～1550 ℃ scope.
When above-mentioned raw materials is mixed, advocate and add in right amount some fluxs again. Especially advocate to add and contain at least a in barium, phosphorus and a boron element compound. Just can obtain to have the luminous compositions of favorable luminance and fine granularity by containing this flux.
As adopt above-mentioned manufacture method, then just can obtain fusion adhesion body by phosphor raw material merely being mixed with dry type or wet type with the vitriol of alkaline-earth metal and burning till, but in general, its 1 particle diameter of alkali earths vitriol is about 1 μ, and will become the above macroparticle of 10 μ after the cohesion, to thoroughly disperse to be unusual difficulty to it, and with the macroparticle of cohesion directly when burning till after fluor and fusing assistant mix, will form huge fusion adhesive particles.In addition, if reduce fusing assistant or weaken the temperature condition that burns till for the generation that prevents this type of situation, then failing has on the contrary but increased with the independent particle of the fine alkali earths vitriol of the complete fusion of fluor adhesion.And these are all not ideal enough on the characteristics of luminescence and coating characteristic.
Now can be described below (to call method for making 2 in the following text) to other manufacture method that the particle diameter with suitable of luminous group of thing of the present invention diminishes size-grade distribution to make.
It is characterized in that, after in the solution that contains the compound that comprises a kind of metallic element that constitutes phosphor matrix at least and alkali earth metal salt, oxalic acid or water-soluble oxalate and sulfuric acid or water-soluble sulfate liquor being added together or respectively, to constitute the throw out of the vitriol of the oxalate of metallic element of above-mentioned parent and above-mentioned alkaline-earth metal, be the major portion of phosphor raw material and then this phosphor raw material burnt till with this throw out.
Rare earth material as fluorescent material is sent out raw material to oxide compound as the master often, but as pre-treatment, generally be that water-solubility rare-earth salt (muriate, nitrate, vitriol etc.) is made the aqueous solution, perhaps oxide compound, oxyhydroxide and charcoal hydrochlorate etc. are dissolved in and make the aqueous solution in the acid (hydrochloric acid, sulfuric acid, nitric acid), thereby in this aqueous solution, add oxalic acid aqueous solution again it is precipitated with rare-earth oxalate, and under 800～1000 ℃, this is fused and make it to form oxide compound.For the fluor Ln that contains a small amount of rare earths activator in the rare earth parent
2O
3: Lu, Ln
2O
2S: Ln especially adopts this processing.
Alkaline-earth metal vitriol is to form after adding sulfuric acid at the aqueous solution of water miscible alkali earths salt (nitrate etc., halogenide) or in oxide compound, carbonate etc. is dissolved in the aqueous solution of hydrochloric acid, nitric acid.Stabilizer pole in water also is difficult to dissolving in acid.
So, containing (comprising the rare earth element of the metallic element that constitutes above-mentioned phosphor matrix) water-solubility rare-earth salt, with in the solution of above-mentioned water-soluble alkali great soil group salt oxalic acid or water-soluble oxalate (ammonium oxalate, diethyl oxalate, the basic metal oxalate, especially ammonium oxalate and dimethyl oxalate are more desirable), and sulfuric acid or water-soluble vitriol (ammonium sulfate, alkali metal sulfates, especially ammonium sulfate is more desirable) solution add together or respectively after, make it to generate the metallic element oxalate that constitutes above-mentioned parent and the throw out of above-mentioned alkaline-earth metal vitriol.When desiring to make it to form precipitation, normally solution is placed under the agitation condition, and just can form the throw out of the granularity of hoping by concentration, oxalic acid and the vitriolic interpolation speed etc. of regulating this agitation condition, solution.
As mentioned above, the precipitation of the metallic element of formation phosphor matrix and the precipitation of alkaline-earth metal vitriol can generate by coprecipitated, or make it progressively to generate, thereby obtain the finely disseminated throw out of each composition, therefore, just can obtain desirable grain matter characteristic, can stably obtain the luminous compositions of excellent in luminous characteristics again.
The throw out that so obtains for example is placed in the thermally resistant container, by burning till the vitriol fusion adhesion that makes above-mentioned fluor and alkaline-earth metal, but this burn till be with above-mentioned same firing condition under carry out.
Again, other manufacture method of the present invention of generation effect same is as follows.
Constitute by fluor or when this activator is solid-solubilized in the twinkler raw material that forms at least a parent stock and mixes with the vitriol of alkaline-earth metal, the vitriol that makes above-mentioned alkaline-earth metal is adhered on the above-mentioned twinkler raw material with the state in the solvent of being dispersed in and forms complex body, make its drying then, just burn till with the arbitrary temperature in 550～1600 ℃ of scopes again and can finish (to call method for making 3 in the following text).
In more detail, when above-mentioned twinkler raw material is mixed with the vitriol of alkaline-earth metal, must be dispersed in this vitriol in the solvent in advance.As the method for this dispersion, also can be only in solvent, to stir, if but mechanically disperse in advance with ball mill, or in solvent, strengthen dispersion by ultrasonic wave, then even more ideal.As solvent, generally be to use water, but special at the twinkler raw material for not have under the situation of water-proof oxide compound, just can use for example organic solvents such as methyl alcohol, ethanol, Virahol.The vitriol that is dispersed in the alkaline-earth metal in the solvent mixes with above-mentioned twinkler raw material with that.This mixing is normally carried out under stirring condition.
So, some has just produced physical adsorption in solvent according to the blended situation for the vitriol of alkaline-earth metal and twinkler raw material, and the particle of twinkler raw material and the vitriol of alkaline-earth metal are adhered equably, generate a species complex.Though the other material does not produce physical adsorption, in this case, to adopt a small amount of organic binder bond be desirable in order to improve sticking power.As this organic binder bond acrylic resin, vinyl acetate resin, polyvinyl butyral resin, synthetic rubber breast, the cruel alkane ketone of polyethylene sheath, polyvinyl alcohol and gelinite etc. are arranged.
The complex body drying that so obtains is handled, and is for example burning till in the thermally resistant container then.This burns till under condition same as described above and carries out.
In manufacture method of the present invention, also can not adopt the vitriol of above-mentioned alkaline-earth metal, in above-mentioned sintering process, also can use the elementary material that replaces alkaline-earth metal vitriol.The vitriol of the so-called alkaline-earth metal of the present invention also contains the elementary material of this class.Mixture as this inorganic salt of the carbonate that alkaline-earth metal is arranged, nitrate of this elementary material or organic salt (acetate, Citrate trianion, oxalate) etc. and vitriol (for example ammonium sulfate etc.).
In addition, the relation between the brightness of firing condition of the present invention and luminous compositions, its typical example is as follows.
Fig. 3 shown, when making luminous compositions of the present invention, the firing temperature of raw material (℃) relation between the relative luminosity (%) during with 253.7nm ultraviolet ray excited.Some A among Fig. 3 is Y
2O
3: Eu fluor (relative luminosity is decided to be 100%), curve 1 is the Y of 50 weight unit
2O
3: the BaSO of Eu fluor and 50 weight unit
4After mechanically mixing, be the situation that raw material burns till with the mixture that obtains, curve 2 is containing as Y 50 weight unit
2O
3: the Y of the Eu of Eu phosphor raw material
2O
3BSO with 50 weight unit
4The situation that the mixture that obtains after the mixing burns till as raw material.As what also can learn from this curve 1, in case the vitriol of fluor and alkaline-earth metal is burnt till, the two just begins the adhesion of fusion successively, and brightness meanwhile also improves.In the time of below 500 ℃, do not observe this phenomenon.In case firing temperature reaches more than 800 ℃, its brightness is also sharply risen (with raw material time compare rise 20%), thereby reaches equal or above this brightness with the brightness of fluor itself.From curve 2,, when then phosphor raw material is grown up as fluor, just begun successively with the fusion adhesion of the vitriol of alkaline-earth metal in case the vitriol of phosphor raw material and alkaline-earth metal is burnt till again.If do not occur any variation between the two, so just can not rise to more than the relative luminosity below 500 ℃ of curve 1, and in the present invention, brightness is then further risen.So in the present invention, firing temperature is on 550 ℃, more preferably more than 800 ℃, is preferably more than 1000 ℃, and effect at this moment is remarkable.In addition from the viewpoint of thermo-efficiency, if common sintering method, though also relevant with firing time, generally be below 1600 ℃, preferably carrying out below 1550 ℃.
Just can obtain luminous compositions of the present invention after having done like this.Material beyond luminous compositions of the present invention and the vitriol that adopts fluor and alkaline-earth metal is also compared with the simple mixing thing of alkaline-earth metal sulphate particles with luminous compositions and fluor that aforesaid method obtains, then demonstrates high brightness.
Fig. 2 shown, the fluor (YGd) during with 253.7nm ultraviolet ray excited
2O
3: illuminant colour (the X value of cie color coordinate) of the above-mentioned simple mixing thing of Eu, this fluor and alkaline-earth metal vitriol and above-mentioned luminous compositions etc. and the relation between the relative luminosity (%).The point A of Fig. 2 shows (YGd)
2O
3: the illuminant colour of Eu fluor and relative luminosity, other the circle seal (●) on the figure represented, on above-mentioned fluor and the figure respectively the mark material of going into at every turn respectively 50 weight unit mix, again with about 12000 ℃ each values of burning till after 4 hours.Again, triangle on figure seal (▲) expression is marking the material of going into carries out the mixture that obtains after the mechanically mixing respectively with each 50% weight unit value on above-mentioned fluor and the figure separately.Also can see clearly from Fig. 2, by above-mentioned fluor and BaSO
4, SrSO
4Each luminous compositions of the present invention of forming is though contain nearly 50%(weight) a large amount of non-luminophore, compare with the some A that constitutes by 100% fluor, its illuminant colour and relative luminosity are all almost constant.Other ZnO, Al have also been used on the other hand
2O
3, BaHPO
4Ca(PO
4)
2, Al
2(SO
4)
3And AlPO
4Deng.Luminous compositions not to be covered among the present invention, its relative luminosity will reduce more than 20～80%, and perhaps illuminant colour also changes, thereby does not reach purpose of the present invention, in addition, does not also resemble and demonstrates unexpected effect the present invention.Again, represented fluor and the BaSO of (▲) seal
4Or SrSO
4Mixture owing to contain these a large amount of non-luminophores, its brightness is compared about reduction by 20% with an A or luminous compositions of the present invention.Though their brightness has confirmed to have the effect of being put down in writing in No. 4069441 communiques of United States Patent (USP), 20% brightness reduces can not be for practical.
Fig. 1 shown, in luminous compositions of the present invention, and when the ratio of components (weight %) that makes fluor and alkaline-earth metal vitriol changes, relative luminosity (%) under 253.7nm is ultraviolet ray excited and the relation between the materials cost reduced rate (%).
The curve 1 of Fig. 1 has shown by Y
2O
3: Eu fluor and BaSO
4Relative luminosity characteristic, the curve 2 of the luminous compositions of forming of the present invention have shown by (YGd)
2O
3: Eu fluor and BaSO
4The relative luminosity characteristic of luminous compositions of the present invention, the curve 3 formed have shown Y
2O
3: Eu fluor and BaSO
4Each relative luminosity characteristic of this prior art of mixture that obtains after mechanically mixing, curve 4 has shown that materials cost attenuating rate (%) is with respect to Y
2O
3: Eu fluor and BaSO
4The relation of composition.Can see clearly by Fig. 1, compare with the prior art shown in the curve 3, curve 1 and 2 represented luminous compositions of the present invention, for example the amount of alkaline-earth metal is a 50%(weight) time, shown brightness improves twenties percent, again, in 80%(weight) time shown brightness improve thirties percent.And when the amount of alkaline-earth metal in 80%(weight) when following, do not contain the brightness that this non-luminophore promptly only depends on fluor itself for the sort of, its brightness has shown identical substantially or has improved nearly 7% this wonderful effect.Moreover materials cost attenuating rate at this moment is up to 76%.
Therefore, from viewpoints such as brightness and materials cost attenuating rates, the content of its alkaline-earth metal vitriol of luminous compositions of the present invention is preferably 5～95%(weight), 10～95%(weight more preferably) scope, and be preferably 25～90%(weight in the practicality).
The vitriol of alkaline-earth metal used in the present invention is the vitriol of barium, strontium and calcium preferably, from above-mentioned effect, proportion, thermostability this some, at least adopt a kind of in barium and the strontium, also be desirable in practicality perhaps with this vitriol that is dominant shape becomes, in addition, at this moment firing temperature is preferably 800～1550 ℃, is 1000～15000 ℃ better.
More than shown the effect when luminous compositions of the present invention being excited, but the electronics line has also shown same effect with ultraviolet ray.Therefore just can see significantly that the present invention does not resemble prior art and only itself uses BaSO by the ultraviolet reflection effect
4Deng.
Luminous compositions of the present invention be actually since which kind of reason just to produce this wondrous effect also indeterminate.Fig. 4-a has shown Y
2O
3: Eu fluor and BaSO
4Particle mixes with each 50% weight and the electron micrograph (3000 times) of the mixture that obtains, Fig. 4-b shown to this mixture burn till and the luminous compositions of the present invention that obtains close an electron micrograph (3000 times).Again, Fig. 4-c has shown (YGd)
2O
3: Eu fluor and BaSO
4Each 50% weight of particle is mixed and the mixture that forms burns till and the electron micrograph (3000 times) of the luminous compositions of the present invention that obtains (more than, the sample of Fig. 4 is measured by evaporation carbon).Fig. 5-a and Fig. 5-b shown, to Y
2O
3: Eu fluor and BaSO
4Particle (each 50% weight) mixes and the mixture that forms, with above-mentioned different condition under burn till respectively and each electron micrograph of the luminous compositions of the present invention that obtains.Again, Fig. 5-c has shown Y
2O
3: Eu phosphor raw material and BaSO
4Carry out coprecipitated and coprecipitated thing that form burns till and the electron micrograph (30,000 times) of the luminous compositions of the present invention that obtains with each weight ratio of 50%.(more than, the sample of Fig. 5 is measured by gold evaporation).
Fig. 5-a and Fig. 5-b are the results who measures with x ray microanalysis instrument, and miliary micropartical is Y
2O
3: the Eu fluor, it is BaSO that the fusion adhesion has these material
4Again, the macrobead among Fig. 5-c also is BaSO
4, it is Y that fusion adheres to its surperficial crystalline particle
2O
3: the Eu fluor.
Fig. 6-a has shown the X ray diffraction model figure of the luminous compositions of the present invention shown in Fig. 4-b, and Fig. 6-b has shown the X ray diffraction model figure of the luminous compositions of the present invention shown in Fig. 4-c.Can think like this from these electron micrographs and X ray diffraction model figure, though luminous compositions of the present invention is made of the part of the vitriol of fluor and alkaline-earth metal or most of particle that forms through the fusion adhesion, it is believed that this composition does not all form both sosoloid.In addition, for obtaining spectrum, Y
2O
3: the spectrum beyond the Eu fluor especially is in BaSO
4: at this moment the spectrum of the ultraviolet portion of Eu fluor do not detect.Therefore, the luminous compositions of the present invention that obtains by above-mentioned manufacture method be with composition formula (Ln, Eu)
2O
3XM
IISO
4(but Ln is at least a among Y, Gd, La, the Lu, and N is alkaline-earth metal and the X positive number for the expression ratio of components) represented.Again, can obtain such notion from above-mentioned example, be that particle that the vitriol of fluor of the present invention and alkaline-earth metal forms through fusion adhesion not only is included in to be preferably in more than 550 ℃ more than 800 ℃ and both is burnt till the back the two is full of the material that boundary is failed to understand shown in Fig. 4-b, comprise that also as shown in Figure 5 both form the agglomerating situation.
When in the present invention, making the vitriol of above-mentioned alkaline-earth metal contain as activator micro-the brightness of resulting luminous compositions with do not contain these micro-situations and be in a ratio of and equate or rose.Can recommend as europium (Eu), plumbous (pb), terbium (Tb), cerium (Ce), manganese (Mn) etc. as the representational example of above-mentioned trace element, especially from above-mentioned effect, be that the occasion of activator is better with at least a in europium and the lead.
As mentioned above, luminous compositions of the present invention can demonstrate high brightness by ultraviolet ray, therefore, adopts this luminous compositions, and is also exceedingly useful according to the luminescent lamp that existing method is made.Luminous compositions particularly of the present invention, brightness is high and the price of the fluor that contains rare earth element and precious metal element is significantly reduced, and therefore, recommends it is actually used on the high color rendering luminescent lamp of this fluor of a large amount of uses.
This that is to say, the fluorescent screen of luminescent lamp comprises the emitting red light material that has the blue-light-emitting material of luminous maximum wavelength, has the green emitting material of luminous maximum wavelength and have luminous maximum wavelength in the scope of 520～560nm in the scope of 595～630nm in the scope of 430～475nm, and at least a of above-mentioned luminophore is made up of luminous compositions of the present invention.As the fluor that is contained in the above-mentioned blue-light-emitting material have the europium activation chloroboric acid calcium series of divalent fluor (for example/Ca
2B
5O
9Cl: Eu
2+), the fluor of the europium of divalent activation alkaline-earth metal aluminate serial (BaMg for example
2Al
16O
27: Eu), the europium of divalent activation alkaline-earth metal halogen-phosphate fluor [aM 7/3 (PO for example
4)
2: bM
IICl
2: Eu
2+(but M
II=Co, Sr, Ba, 1≤a/b≤3)], as the fluor that is contained in the above-mentioned green emitting material cerium is arranged, the fluor of terbium activation lanthanum orthophosphate series (LaPO for example
4: Ce, Tb), the fluor of cerium terbium activation alkaline-earth metal borate series [nM for example
IIO
2O
3: Ce, Tb(but M
II=Mg, Zn, 0＜n≤2), GdMgB
5O
10: Ce, Tb], terbium activation alkaline-earth metal Cerium aluminate salt fluor [for example (Ce, Tb) M
IIAl
11O
19(but M
II=MgZn)], cerium terbium activation rare earth class silicate phosphor [LnSiO for example
5Ce, Tb(but Ln=Y, Gd, La)], the fluor [Ln for example of europium activation rare-earth oxide series is arranged as the fluor that is contained in the above-mentioned emitting red light material
2O
3Eu(Ln=Y, Gd, La)], more than be proposed as representational fluor respectively.Moreover, also can be added in the blue-greenish colour luminophore that has peak luminous wavelength in 480～500nm scope in order to obtain color rendering.The europium activated strontium chlorate MClO 3 fluorescent substance [4SrOnAl for example that divalent is arranged as the fluor that is contained in this blue-greenish colour luminophore
2O
3: Eu
2+Europium activation alkaline-earth metal borophosphate fluor [the routine mM of (but 5≤n≤8), divalent
IIO(1-n) P
2O
5NB
2O
3=Eu
2+(but M
II=Cu, Sr, Ba, 1.75≤m≤2.30,0.05≤n≤0.23)], these can be used as representational example and recommend.
Adopted the luminous compositions of the present invention that the vitriol fusion of at least a above-mentioned fluor and alkaline-earth metal adhesion is formed that the usage quantity of above-mentioned fluor is reduced significantly.Recommendablely from this purpose be, luminous compositions of the present invention as above-mentioned fluor, or contains the rare earth element that constitutes parent element, or selects to contain the fluor as the oxide compound series of a large amount of rare earth elements of activator.That is, so-called this fluor is meant that europium activation rare-earth oxide is the fluor of thing and the fluor of cerium terbium activation rare earth class silicate series etc.
Again, the wonderful effect of luminous compositions of the present invention is the brightness that is not only to improve the fluor that fusion adhered, and for making the effect of also not brought luminous efficiency to improve through other fluor of fusion adhesion of mechanically mixing with luminous compositions of the present invention.For example, have (LnEu) as luminous compositions of the present invention
2O
3BaSO
4The high color rendering luminescent lamp of the present invention of the fluorescent screen that mixes with above-mentioned green emitting fluor and above-mentioned blue-light-emitting fluorescent material and obtain is in order to obtain and not contain above-mentioned BaSO
4The identical illuminant colour of existing high color rendering fluor, not only (LnEu)
2O
3The usage quantity of fluor has reduced, and the usage quantity of other green emitting fluor and blue-light-emitting fluorescent material also can reduce simultaneously.This example can illustrate with embodiment.Recommendable according to this fact is should suitably select in high color rendering luminescent lamp of the present invention and the vitriol of alkaline-earth metal fluor the most stable or that more easily make luminous compositions of the present invention.The representative substances of this fluor activates the fluor of rare-earth oxide series for the europium that shows emitting red light.Therefore, embodiment shown below has just adopted the luminescent lamp of the luminous compositions of the present invention that uses this fluor to describe, but the present invention is not subjected to the restriction of these embodiment.
Below, the present invention will be described in more detail by enumerating some embodiment.
Adopt the gadolinium sesquioxide (Gd of 76 weight unit
2O
3), the yttrium oxide (Y of 20 weight unit
2O
3), the europium sesquioxide (Eu of 4 weight unit
2O
3), as the oxalate precipitation thing, under 1000 ℃, these materials are carried out 3 hours burning till with this then, thereby make by (Gd, Y, Eu
2) O
3Represented oxide compound.Then 50 weight unit this (Gd, Y, Eu)
2O
3Barium sulfate (BaSO with 50 weight unit
4Superfine reagent) mixes, add the fusing assistant (BaCl of 1% weight
22H
2The H of O and 0.1% weight
3BO
4), be filled to behind the thorough mixing in the crucible and under 1200 ℃ temperature, burnt till 4 hours.Again through clean dry just can obtain luminous compositions of the present invention (Y, Gd, Eu)
2O
3BaSO
4[shown electron micrograph (3000 times) among Fig. 4-c.Again, Fig. 6-b has shown the X ray diffraction model].On the other hand, under same condition only to above-mentioned oxide compound (Gd, Y, Eu)
2O
3The fluor that burns till the processing gained is as standard substance, be filled into above-mentioned luminous compositions and these standard substance in the quartz container respectively, thereby with the ultraviolet ray of 253.7nm shine measure luminosity and illuminant colour (below, claim thisly to be determined as ultraviolet ray and to measure), at this moment find both on the point of luminosity and illuminant colour (x/y=0.650/0.346) completely without difference.Characteristic when with same manufacture method ratio of components being changed is indicated on the curve 2 of Fig. 1.
The yttrium oxide (Y of 95 weight unit
2O
3), the europium sesquioxide (Eu of 5 weight unit
2O
3) as starting raw material, other all use the method identical with embodiment 1, thereby made by (Y, Eu)
2O
3Represented oxide compound, then, the certain ratio of mixture (weight %) shown in the according to the form below this (Y, Eu)
2Add barium sulfate (BaSO among the O
4), and under 1400 ℃, burnt till 4 hours, other all adopt the method identical with embodiment 1, thereby obtain with the luminous compositions of the present invention of the corresponding ratio of components of each ratio of mixture (weight %) (Y, Eu)
2O
3XBaSO
4[electron micrograph (3000 times) of the 3rd product of the present invention of table 1 is presented at Fig. 4-b.Shown the X ray diffraction model on Fig. 6-a] again.
Only use above-mentioned oxide compound, produce standard substance similarly to Example 1, relative luminosity and materials cost attenuating volume that each ultraviolet ray is measured are presented at following table.Again, illuminant colour does not at this moment change completely.Again, materials cost attenuating volume is promptly (YEu) by the amount of money that can buy each material usually
2O
3Materials cost in 4200 yen/kilogram, BaSO
4Materials cost calculate in 2000 yen/kilogram.
Embodiment 3
The yttrium oxide (Y of 94.6 weight unit
2O
3), the europium sesquioxide (Eu of 5.4 weight unit
2O
3) as starting raw material, other all adopt the method identical with embodiment 1, make by (Y.Eu)
2O
3Represented oxide compound.Then 50 weight unit this (Y, Eu)
2O
3Barium sulfate (BaSO with 50 weight unit
4) mix, adopt then the method identical with embodiment 2 make luminous compositions of the present invention (Y, Eu)
2O
3(BaSO
4).On the other hand, following of same condition to above-mentioned oxide compound (Y, Eu)
2O
3The fluor that burns till processing and obtain is as standard substance, after above-mentioned luminous compositions and these standard substance are excited as fluorescent screen so that illuminant colour and luminosity are measured, found that both on illuminant colour (X/Y=0.64/0.353) and luminosity completely without difference.
Again, to the above-mentioned standard substance of 50 weight unit (Y, Eu)
2O
3Barium sulfate (the BaSO of fluor and 50 weight unit
4) thorough mixing and the mixture that obtains measure under these conditions, found that illuminant colour is constant, but luminosity reduced significantly.
Shown in the embodiment 2 of 50 weight unit (Y, Eu)
2O
3Strontium Sulphate (the SrSO of oxide compound and 50 weight unit
4) in add fusing assistant, behind the thorough mixing, be filled in the crucible, under 1350 ℃ temperature, burnt till 4 hours, then clean and dry, thus obtain luminous compositions of the present invention (Y, Eu)
2O
5SrSO
4To the standard substance of this luminous compositions and embodiment 2 (Y, Eu)
2O
3Fluor is done ultraviolet ray and is measured, and found that both complete indifferences on luminosity and illuminant colour.
The terbium of 70 weight unit activation yttrium aluminate salt fluor (Y
2Al
5O
12: Tb) with the barium sulfate (BaSO of 30 weight unit
4) mix, add the fusing assistant (BaCl of 1 weight unit again
22H
2The H of O and 0.1 weight unit
2BO
3), under 1200 ℃ temperature, burnt till 2 hours again after fully mixed, then clean and dry, thereby obtain luminous compositions of the present invention.This luminous compositions is with ultraviolet ray (253.7nm) luminosity when exciting, with Y
3Al
5O
12: the Tb fluor is to show 83% at 100% o'clock.Again, the luminosity of the simple mixing thing before above-mentioned the burning till is 62%.
Embodiment 6
The europium of 70 weight unit activation oxygen yttrium sulfide fluor (Y
2O
2S: Eu) barium sulfate with 30 weight unit mixes, and adds fusing assistant (Trilithium phosphate of 1 weight unit) again, thereby then adopts way similarly to Example 5 to obtain luminous compositions of the present invention.This luminous compositions is with ultraviolet ray (253.7nm) luminosity when exciting, with Y
2O
3S: the Eu fluor is 100% to have shown 101%.Yet the luminosity of the simple mixture before above-mentioned the burning till is 67%.
Embodiment 7
The terbium of 70 weight unit activation oxygen yttrium sulfide fluor (Y
2SiO
5: Tb) with the barium sulfate (BaSO of 30 weight unit
4) mix, add the fusing assistant (Li of 1 weight unit again
2B
4O
7) under 1300 ℃ temperature, burnt till 2 hours more after fully mixed, then clean and dry, thereby obtain luminous compositions of the present invention.This luminous compositions is with ultraviolet ray (253.7nm) luminosity when exciting, with Y
2SiO
5: the Tb fluor is to show 110% at 100% o'clock.Yet the luminosity of the simple mixing thing before above-mentioned the burning till is 60%.
Embodiment 8
The terbium of 50 weight unit activation oxygen gadolinium sulfide fluor (Gd
2O
2S: Tb) with the barium sulfate (BaSO of 50 weight unit
4) mix, thereby adopt the way identical to obtain luminous compositions of the present invention then with embodiment 5.This luminous compositions is with ultraviolet ray (253.7nm) luminosity when exciting, with Gd
2O
2S: the Tb fluor is to show 91% at 100% o'clock.Again, the luminosity of the simple mixing thing before above-mentioned the burning till is 65%.
Embodiment 9
The europium of 50 weight unit activation oxygen yttrium sulfide vanadate fluor (YVO
4: Eu) with the barium sulfate (BaSO of 50 weight unit
4Thereby) take after mixing the way identical with embodiment 5 to obtain luminous compositions of the present invention.This luminous compositions is with ultraviolet ray (253.7nm) luminosity when exciting, with YVO
4: the Eu fluor is to show 83% at 100% o'clock.
Liquid medicine A liquid, B liquid, C liquid and D liquid have been prepared as follows.
A liquid: 950 gram Y
2O
350 gram Eu
2O
3Be dissolved in the hydrochloric acid of specified rate and alkene is released to 10 liters.
B liquid: 1000 gram BaCl
22H
2O is dissolved in the water and is diluted to 5 liters.
C liquid: 600 gram oxalic acid are dissolved in the 3 intensification water.
D liquid: 500 gram sulfuric acid are made 3 liters of dilution heat of sulfuric acid.
In the mixed solution of A liquid and B liquid, slowly add D liquid while stirring.After adding end, continue to add at leisure C liquid.After the interpolation, through abundant churning time, then the precipitation resultant that is obtained is washed, dewatered after cleaning, and in the quartzy stove formula container of packing into, in air, fuse to make it to become in 3 hours and burn till raw material with 1000 ℃ temperature.
Add fusing assistant (0.1% BaCl in the raw material above-mentioned burning till
22H
2O and 0.1% H
3BO
3) and carry out thorough mixing, be filled in the crucible and under 1400 ℃ temperature, burnt till 4 hours.After this, take out and wash fully, dehydrate after cleaning, with just having formed luminous compositions after the screening of 150 purpose screen clothes.
Measure above-mentioned granularity of burning till raw material and luminous compositions, its result is presented at table 2.
Embodiment 11
In the mixture of the A of embodiment 10 solution and B solution,, will make and burn till raw material and luminous compositions through the precipitation resultant that fully stirs the back gained according to similarly to Example 10 step then while stirring the mixed solution that slowly adds C liquid and D liquid.
Comparative example 1
In the A of embodiment 10 liquid, slowly add C liquid, burn till raw material according to step acquisition similarly to Example 10 then while stirring.
This of 50 weight unit burn till raw material (Y, Eu)
2O
3The commercially available BaSO that has passed through 150 eye mesh screens with 50 weight unit
4And fusing assistant (1% BaCl
22H
2O and 0.2 H
3BO
3) add together, be filled in the crucible, under the condition identical, make luminous compositions then with embodiment 10.The granularity of burning till raw material and luminous compositions is illustrated in table 2.
Embodiment 12
The throw out that obtains among the embodiment 10 is washed and dewatered, add fusing assistant (0.5% BaCl then
22H
2O and 0.1%H
3BO
3), behind the thorough mixing, in quartzy stove formula container, under 1400 ℃ temperature, burnt till 4 hours, wash again, carry out drying after cleaning, with the screening of 150 purpose screen clothes, obtained luminous compositions then.The granularity of burning till raw material and luminous compositions is illustrated in table 2.
Embodiment 13
In the ball mill that water and aluminium alms bowl are housed in advance to barium sulfate (BaSO
4) carry out 40 minutes dispersion treatment, then the BaSO that contains 30 weight unit
4Slurry drop in the water, while stir drop into hereinto again 70 weight unit (Y, Eu)
2O
3Coprecipitated oxide compound.The diluting soln that adds the acrylic latex (Japanese propylene (strain) HA-24) of 0.5 weight unit after doing further to stir again.Then to the complex body that is obtained dewater, dry and screening, add fusing assistant (0.1% BaCl then
22H
2O and 0.3% and H
3BO
3), refill after fully mixed in the crucible, under 1350 ℃ temperature, burnt till 4 hours.Constituent after burning till is taken out from crucible, fully dehydrate again after the washing, with just having obtained luminous compositions of the present invention after the screening of 150 purpose screen clothes.
Drop into the commercially available BaSO of 30 weight unit in the solution that after the gelatin of 0.5 weight unit fully is dissolved in warm water, obtains
4, through drop into again after fully stirring 70 weight unit (Y, Eu)
2O
3Coprecipitated oxide compound adds the solution of 0.3 weight unit gum Arabic again after further stirring.After this, to the complex body that is obtained dewater, dry, sieve, sneak into fusing assistant, burn till etc., done just to have obtained luminous compositions of the present invention after the processing similarly to Example 13.
Comparative example 2
70 weight unit (Y, Eu)
2O
3Coprecipitated oxide compound and the commercially available BaSO that passes through 150 sieve meshes of 30 weight unit
4And fusing assistant (1% BaCl
22H
2O and 0.2% H
3BO
3) mix after, the mixture of gained is filled into crucible, under the condition identical, burn till then, thereby obtained luminous compositions with embodiment 3.
More than, granularity, particle diameter and the brightness of each luminous compositions of embodiment 13,14, comparative example 2 are measured, its result is as shown in table 3.
Can see clearly that from table 3 luminous compositions of the present invention has shown excellent luminance, and be the narrow luminous compositions of a kind of particle size distribution.
The ammonium sulfate of the barium acetate of 41 weight unit and 21 weight unit add in the blended mixture through pulverizing 38 weight unit (Y, Eu)
2O
3Coprecipitated oxide compound and the rib flux (BaCl2H of 1 weight %
2O and 0.3% H
3BO
3), be filled into crucible after fully mixed, under the condition identical, burn till then, thereby obtain the luminous compositions of the present invention formed by europium active oxidation yttrium fluor and barium sulfate with embodiment 13.
Remove to adopt 27 weight unit lime carbonate, 37 weight unit ammonium sulfate and (Y, Eu)
2O
3Coprecipitated oxide compound outside, other all takes the 15 identical ways with embodiment, thereby has obtained the luminous compositions of the present invention be made up of europium active oxidation yttrium fluor and calcium sulfate.
Adopt the ammonium sulfate of strontium nitrate, 25 weight unit of 40 weight unit and 35 weight unit (Y, Eu)
2O
3Coprecipitated oxide compound, all take way similarly to Example 15 in addition, thereby obtain the luminous compositions of the present invention formed by europium active oxidation yttrium fluor and Strontium Sulphate.
Comparative example 3
Adopt the Strontium Sulphate of 50 weight unit and 50 weight unit (Y, Eu)
2O
3Coprecipitated oxide compound, other all adopt the way identical with embodiment 15, thereby obtain the luminous compositions with embodiment 17 same compositions.
More than the granularity and the particle diameter of each luminous compositions of embodiment 15,16,17 and comparative example 3 are measured, its result is as shown in table 4.
As can seeing clearly from table 4, the luminous compositions of the present invention by this method for making has obtained narrower particle size distribution.
Embodiment 18
The luminous compositions of the present invention shown in the embodiment 1 of 43.5 weight unit (Y, E)
2O
3BaSO
4(X/Y=0.657/0.348) emitting red light composition, the LaPO of 33.7 weight unit
4: Ce, the green emitting composition of Tb fluor (X/Y=0.359/0.547) and the Ca of 22.8 weight unit
2B
5O
9Cl: the blue-light-emitting composition of Eu fluor (X/Y=0.134/0.094) carries out thorough mixing, use this mixing phosphor to make coating liquid, in Glass tubing, apply this liquid then, make coating amount reach about 4mg/cm, produce luminescent lamp by existing method then as mixing phosphor.This luminescent lamp has shown white luminous higher color rendering in the illuminant colour (X/Y=0/345/0.347), and its brightness removes does not use BaSO
4In addition, identical luminescent lamp (Br=100%) is shown as 99%.
The luminous compositions (Y of 50 weight unit
0.93, Eu
0.637)
2O
3BaSO
4Emitting red light composition, the LaPO of 35 weight unit
4: Ce, the green emitting composition of Tb fluor and 15 weight unit (Sr, Ca)
5(PO
4) Cl: Eu
2+The blue-light-emitting composition of fluor carries out thorough mixing, makes coating liquid with this mixing phosphor then, then is coated in the Glass tubing, thereby makes 30 watts white luminous luminescent lamp.Coating amount is 4mg/cm.The luminous efficiency that this luminescent lamp shows is 711m/w, and drilling look evaluation number is 82.
Adopt the luminous compositions (Y of 35 weight unit
0.1Gd
0.87Eu
0.03)
2O
3BaSO
4The emitting red light composition and the LaPO of 35 weight unit
4: Ce, the green emitting composition of Tb fluor and the BaMg of 15 weight unit
2Al
16O
27: the blue-light-emitting composition of Eu fluor has made white luminous luminescent lamp similarly to Example 16.The luminous efficiency that this luminescent lamp shows is 691m/w, and drilling look evaluation number is 83.
Embodiment 21
Adopt the luminous compositions (Gd of 50 weight unit
0.955Eu
0.045)
2O
30.7BaSO
4Emitting red light composition, the LaPO of 30 weight unit
4: Ce, the green emitting composition of Tb fluor, the Ca of 15 weight unit
2B
5O
9Cl; Eu
2+The blue-light-emitting composition of fluor and the 2(Ba of 30 weight unit, Ca, Sr) O0.9P
2O
50.1B
2O
3The blue green emitting composition of fluor is made white luminous luminescent lamp similarly to Example 16.The luminous efficiency that this luminescent lamp shows is 70ml/w, and drilling look evaluation number is 82.
Comparative example 4
Adopt (the Y of 37 weight unit
0.693Eu
0.037)
2O
3The emitting red light composition of fluor, the LaPO of 43 weight unit
4: Ce, the green emitting composition of Tb fluor and 20 weight unit (Sr, Ca)
5(PO
4)
3Cl: the Eu fluor, the method that useful and embodiment 16 are identical has made and has had the white luminous luminescent lamp of well-known ratio of components in the past.The luminous efficiency that this luminescent lamp shows is 701m/w, and drilling look evaluation number is 82.
Comparative example 5
(the Y of 25 weight unit
0.963, Eu
0.037)
2O
3The LaPO of fluor, 35 weight unit
4: Ce, Tb fluor, 15 weight unit (Sr, Ca)
5(PO
4)
3Cl: Eu
2+And the BaSO of 25 weight unit
4(superfine reagent) mixes, and adopts the method identical with embodiment 16, made white luminous luminescent lamp.The luminous efficiency that this luminescent lamp shows is 591m/w, and drilling look evaluation number is 79, and lightness is insufficient, drills look evaluation number and has also reduced.
Table 1
The ratio of mixture of luminous compositions (weight %) luminescent material is relatively taken reduction
№
(Y, Eu)
2O
3B
aSO
4Brightness (%) amount of money (yen/kg) rate (%)
1 standard substance 100 0 100 00
2 the present invention's product 90 10 106 4,000 9.5
3 the present invention's product 50 50 106 20,000 47.5
4 the present invention's product 30 70 105 28,000 66.7
5 the present invention's product 20 80 103 32,000 76.2
6 the present invention's product 10 90 95 36,000 85.7
7 comparative examples 0 100 0 40,000 95.2
Table 2
Embodiment
Comparative example 1
10 11 12
（Y，Eu）
2O
3BaSO
4
-
The particle diameter d of central authorities
505.1 μ 6.1 μ 4.9 μ 17.0 μ
-
Burn median size d5.5 μ 6.5 μ 5.7 μ 20.5 μ
Become
Former size-grade distribution
Material～4 μ 26% 27%-35% 0%
4～16μ 72% 71% 63% 37%
16μ～ 2% 2% - 2% 63%
The particle diameter d of central authorities
508.2 μ 8.4 μ 8.5 μ 6.3 μ
Send out median size d8.5 μ 8.8 μ 8.9 μ 11.3 μ
The light size-grade distribution
Group
Become～5 μ 17% 18% 18% 33%
16μ～ 2% 5% 6% 18%
3
Embodiment 13 embodiment 14 comparative examples 2
The particle diameter d of central authorities
506.5 6.7 7.1
Median size 7.8 8.4 12.2
Size-grade distribution
0～4μ 145.% 17.7% 18.2%
4～16μ 80.6% 77.7% 59.2%
16 μ above 4.9% 4.6% 22.6%
Powder brightness 102 101 100
Film brightness 107% 105% 100%
Table 4
Embodiment 15 embodiment 16 embodiment 17 comparative examples 3
The particle diameter d of central authorities
509.9 10.0 9.2 8.5
Size-grade distribution
0～5μ 12% 11% 13% 18%
5～15μ 68% 71% 75% 56%
More than 15 20% 18% 12% 20%
Claims (18)
1, a kind of luminous compositions, it is that the alkaline earth metal sulphate of 5% (weight)-95% (weight) is melting the particle that forms that this constituent contains by oxide based fluor and content, described oxide based fluor contains at least a in rare earth element and the precious metal element, described alkaline earth metal sulphate contains at least a in barium, strontium and the calcium, and contains the trace element as activator on demand.
2, luminous compositions according to claim 1, the content that it is characterized in that above-mentioned vitriol is 10～95%(weight).
3, luminous compositions according to claim 1 is characterized in that above-mentioned alkaline-earth metal is at least a in barium and the strontium, or as main.
4, luminous compositions according to claim 1 is characterized in that above-mentioned fluor is the rare-earth oxide fluor that contains as the europium of activator.
5, luminous compositions according to claim 1 is characterized in that above-mentioned trace element is at least a in europium and the lead.
6, a kind of manufacture method of luminous compositions, it is characterized in that, is 5%(weight with at least a oxide based fluor or the phosphor raw material that contain in rare earth element and the precious metal element with content)-95%(weight), contain barium, at least a in strontium and the calcium, and contain state on demand as both coexistences of alkaline earth metal sulphate of the trace element of activator, fluor or its activator be placed on carry out molten admittedly at least a parent stock and this phosphor raw material of obtaining etc. mechanically mix with alkaline earth metal sulphate, adjust, in 550 ℃-1600 ℃ temperature range, burn till.
7, the manufacture method of luminous compositions according to claim 6 is characterized in that adding a kind of compound at least a in barium, phosphorus and the boron that contains as fusing assistant.
8, the manufacture method of luminous compositions according to claim 6, the content that it is characterized in that above-mentioned alkaline earth metal sulphate is 10～95%(weight).
9, the manufacture method of luminous compositions according to claim 6 is characterized in that above-mentioned burning till is to carry out under arbitrary temperature of 800-1550 ℃ of scope.
10, the manufacture method of luminous compositions according to claim 6, it is characterized in that in containing the two the aqueous solution of the compound that comprises a kind of metallic element that constitutes phosphor matrix at least and alkaline earth salt oxalic acid or water-soluble oxalate and sulfuric acid or water-soluble sulfate liquor are added together or respectively, with the oxalate of the metallic element of the above-mentioned formation parent of acquisition like this and the throw out of above-mentioned alkaline earth metal sulphate is the major portion of phosphor raw material, and this phosphor raw material is burnt till.
11, the manufacture method of luminous compositions according to claim 6, that it is characterized in that to constitute by fluor or carry out twinkler raw material that solid solution obtains at least a parent stock when mixing with the vitriol of alkaline-earth metal by its activator is placed on, the vitriol of above-mentioned alkaline-earth metal is got on to be adhered to above-mentioned phosphor raw material under the dispersive state in solvent, thereby formation complex body, be dried again, and then burn till.
12, the manufacture method of luminous compositions according to claim 6, the vitriol that it is characterized in that above-mentioned alkaline-earth metal are to be made of its elementary material.
13, the manufacture method of luminous compositions according to claim 12 is characterized in that above-mentioned elementary material is that alkaline earth metal compounds and ammonium sulfate are formed.
14, a kind of luminous compositions is used for the purposes of luminescent lamp, it is characterized in that, the luminous compositions of the particle that contains the vitriol fusion adhesion back formation that makes described oxide based fluor of claim 1 and alkaline-earth metal is included in the fluorescent screen as luminophore.
15, luminous compositions according to claim 14 is used for the purposes of luminescent lamp, it is characterized in that above-mentioned fluorescent screen contains the blue-light-emitting material that has luminous maximum wavelength in 430～475nm scope, the emitting red light material that has the green emitting material of luminous maximum wavelength and have luminous maximum wavelength in 520～560nm scope in 595～630nm scope.
16, luminous compositions according to claim 15 is used for the purposes of luminescent lamp, it is characterized in that above-mentioned fluorescent screen further contains the blue-greenish colour luminophore that has luminous maximum wavelength in 480～500nm scope.
17, luminous compositions according to claim 15 is used for the purposes of luminescent lamp, it is characterized in that above-mentioned emitting red light material is made up of the luminous compositions that contains a kind of particle, this particle is to form by making to contain as the rare earth oxide fluor of the europium of activator and the vitriol fusion adhesion of alkaline-earth metal.
18, luminous compositions according to claim 14 is used for the purposes of luminescent lamp, it is characterized in that above-mentioned fluor is the oxide based fluor that contains as the rare earth element that constitutes parent element.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28114685 | 1985-12-16 | ||
| JP281.146/85 | 1985-12-16 | ||
| JP87.174/86 | 1986-04-17 | ||
| JP138.343/86 | 1986-06-16 | ||
| JP13834386 | 1986-06-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86108231A CN86108231A (en) | 1987-07-01 |
| CN1020743C true CN1020743C (en) | 1993-05-19 |
Family
ID=26471400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86108231 Expired - Fee Related CN1020743C (en) | 1985-12-16 | 1986-12-15 | Luminous compositions and process for their prepn. and fluorescent lamp using the compositions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1020743C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1591767B (en) * | 2003-05-22 | 2011-04-13 | 通用电气公司 | Fluorescent lamp |
-
1986
- 1986-12-15 CN CN 86108231 patent/CN1020743C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1591767B (en) * | 2003-05-22 | 2011-04-13 | 通用电气公司 | Fluorescent lamp |
Also Published As
| Publication number | Publication date |
|---|---|
| CN86108231A (en) | 1987-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1981018B (en) | Fluorescent substance, light-emitting element using the same, image display device, and illuminating device | |
| CN1211454C (en) | Red light-emitting afterglow photoluminescence phosphor and afterglow lamp using the phosphor | |
| CN1561549A (en) | Light emitting element and light emitting device using this | |
| CN1108681A (en) | Fluorescentor, cathode ray tube, fluorescent lamp and radiation intensifying paper | |
| CN103328607A (en) | Fluorescent body for light-emitting device, method for producing same, and light-emitting device using same | |
| CN1224658C (en) | Process for producing fluorescent metal oxide material | |
| CN1906270A (en) | Light emitting devices with mixed phosphors | |
| JP4810152B2 (en) | Red phosphor and white light emitting device | |
| CN1020743C (en) | Luminous compositions and process for their prepn. and fluorescent lamp using the compositions | |
| JP2001172623A (en) | Fluorescent substance and fluorescent lamp using the same | |
| CN113583661A (en) | Spheroidal fluoride fluorescent powder, preparation method thereof, mixture and light-emitting device | |
| JPH04234480A (en) | Red light emitting phosphor having adherent pigment and its manufacture | |
| CN1009513B (en) | Cathode ray tube | |
| JP2757889B2 (en) | Method for producing luminescent composition | |
| JP2002188084A (en) | Red light-emitting phosphor and light-emitting apparatus using the same | |
| CN1091792C (en) | Long persistence luminous sulfide material and producing method | |
| JP4886221B2 (en) | Method for manufacturing light emitting device | |
| CN102399554A (en) | Nitride red luminescence material, and luminescent part and luminescent device containing the same | |
| US2589513A (en) | Method of making titanium activated calcium magnesium silicate phosphor | |
| JP7345949B1 (en) | Method for manufacturing phosphorescent particles | |
| CN110590361A (en) | Composite phase fluorescent ceramic and preparation method and application thereof | |
| CN109777422A (en) | Suitable for purple light excited blue colour fluorescent powder and preparation method thereof and light emitting device | |
| CN105441075B (en) | A kind of barium pyrophosphate titanium fluorescent material and preparation method thereof | |
| CN1846291A (en) | Light emitting devices having sulfoselenide fluorescent phosphors | |
| KR100248599B1 (en) | Method of manufacturing a green phosphor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |