TW201229210A - Method for producing manganese-activated germanate phosphor - Google Patents

Abstract

Provided is a method for producing a manganese-activated germanate phosphor that has a high emission intensity and is represented by general formula (1), a(Mg1-xM1x)ObMgF2c{(Ge1-yM2y)O2}:nMn4+ (1) the method for producing a manganese-activated germanate phosphor being characterized in that a mixed slurry is prepared by mixing a dispersant with magnesium fluoride, a magnesium compound other than magnesium fluoride, a germanium compound, a manganese compound, and one or more compounds containing additional elements selected from the above-mentioned M1 elements and M2 elements added as necessary, this starting mixed slurry is wet mixed using a media mill, the resulting uniformly mixed slurry is spray dried to obtain a reaction precursor, and this reaction precursor is fired.

Description

201229210 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a manganese-activated yanoate phosphor which is useful as a red phosphor. [Prior Art] In recent years, it has been known that a blue dipole system is put into practical use and a white light-emitting diode using the diode as a light-emitting source is studied. The light-emitting diode system has the advantage of being so lightweight and not using mercury to have a long life. It is known to apply, for example, a blue light-emitting element to a white light-emitting diode of Y3Ah〇i2: Ce. However, the light-emitting diode system is strictly white, and it is a mixed blue-green white. Therefore, it is proposed to mix Y3Al5〇i2 : Ce and a red phosphor that absorbs blue light and emits red fluorescence to adjust the color tone. The report on the red phosphor that emits red light and absorbs blue light is mostly an organic material, but the inorganic material is less. On the other hand, as a general red fluorescent system, an inorganic material such as an oxide phosphor, an oxysulfide phosphor, a sulfide phosphor, or a nitride phosphor is proposed, and a manganese activated decanoate is also proposed. Fluorescent body. As a general manufacturing method of a manganese-activated yanoate phosphor, it is known to mix magnesium oxide and magnesium fluoride by using a ball mill or the like, manganese, manganese activated 4' at 1 000 to 120, yttrium oxide and carbonic acid'. , 1 2 0 0 C 'A mixture obtained by firing, a phthalate phosphor.

Performing the firing In addition, the mill is mixed with the method of 201229210. Further, in the following Patent Document 2, it is proposed to use a magnesium oxide as a magnesium compound to regularly or irregularly shake a container to which magnesium oxide, magnesium fluoride, gallium oxide and manganese compounds are added, or to externally stir. Means for stirring a raw material and simultaneously calcining to obtain a manganese-activated decanoic acid phosphor in which primary particles become large and aggregates of fine particles are not contained. Conventionally, a manganese-activated decanoic acid fluorescent system is obtained by mixing a raw material in a dry state or a wet state in a plurality of states, and firing a homogeneous mixture to obtain a manganese-activated decanoic acid phosphor. The fluorescent system thus obtained has a problem in light emission intensity, and the quantum yield rate also becomes low. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. Accordingly, the present invention provides a process that facilitates the industrial manufacture of manganese activated phthalate phosphors that provide improved performance over conventional manganese activated phthalate phosphors. [Means for Solving the Problem] The present invention provides a method for producing a manganese-activated strontium silicate phosphor by the following formula (1): MMghMlOO.bMgFpcM (GeiyM2y)CM:nMn"(1) 4 s 201229210 (In the chemical formula, Ml Sunben _ group..., one or two or more elements, and M2 means one selected from the group of si, Sn, and Pb, and one of the following; Or two or more elements: a indicates 〇 <..., b indicates 〇.5...4, c indicates 〇8", and the system does not G. GG1S 〇· 〇5, χ indicates

SyS 0.28. A method for producing a manganese-activated strontium hydride phosphor that is not a scent of a scent, which is characterized in that it contains a compound derived from magnesium fluoride, a fluorinated town, a compound, a stimulating compound, and It is prepared by mixing one or more kinds of the additive element-containing compound of the additive element, which is added with the above-mentioned lanthanum element M2 7L, in a mixed slurry of the dispersion medium, and mixing the raw material by a media roll mill. The t-body' is subjected to wet mixing, and the slurry is uniformly mixed until it is attached to the spray drying method to become a reaction precursor to "fire" the reaction precursor. [Effect of the Invention] According to the present invention, a red light manganese activated strontium silicate phosphor having high luminescence intensity can be obtained by an industrially advantageous method. [Embodiment] The present invention will be described below based on its preferred embodiments. The vigorously activated maltorite fluorescent system obtained by the present production method is excited by blue light to emit red light. Specifically, the excitation is performed by excitation light of at least 270 to 550 nm, preferably 380 to 490 nm. Further, in the region of 580 to 750 ηιη, preferably 600 to 700 nm, there is a light-emitting band (that is, having a red spectrum). 201229210 The manganese-activated decanoate fluorescent system obtained by the present production method is represented by the following general formula (1). a ( Mgi-xMlx) 〇 . bMgFa · c { ( Ge.-vM2y) 〇 2 } : nMn4+ ( 1 ) The M1 in the chemical formula of the formula (1) represents Zn, Cu, Cd, Ca,

One or more elements selected from the group of Hg, Sr, and Ba, and M2 means the group selected by Si, Sn, and Pb! Species or more than two elements. The above-mentioned M1 element is partially substituted with a magnesium atom and is contained in a manganese-activated decanoate phosphor to further increase the luminescence height, and the M2 element system is also partially substituted into ruthenium as needed. An atom and an element which is contained in a manganese-activated strontium hydride phosphor to further increase the luminescence height. 3 of the formula (1) is 0 0<a$4, preferably $ 3. 4 ' b 〇. 5$ 4, $1.2, best county n $4, preferably 〇.6$bS3,c Department 0.8 core c

System 3, which will contain magnesium compounds other than magnesium fluoride and magnesium fluoride,

The polymer ' is added to the mixed slurry of the spray snail to be prepared, and is wet-mixed by the medium crusher 5, and the mixture is uniformly mixed and sprayed to form a reaction precursor, and the reaction is fired.

6 S 201229210 First, the process of the body. That is to say, the slurry preparation process and the firing process are uniformly mixed. The manufacturing method generally comprises a (A and B) spray drying process and (in the case of a uniform mixed slurry of (A), magnesium (4) (hereinafter, only: chemical: town, gasification town compound, manganese compound and Adding force due to need."), 锗,,, ', plus the addition of elemental characters, evenly mixed with the dispersion medium ° Hook mixed slurry. 〖The original shaking is evenly mixed by the uniform mixture can be In the case of temperature-changing cross-baked B ^ easy view, it is best to use magnesium as the ideal physical property system. The average J is only 10 or less in m, especially 〇~1 A m. · 乍 is a magnesium compound except oxidation. In addition to magnesium, the (C) firing process described later can also be converted into magnesium oxide and used as a poorly soluble or insoluble agent for a dispersion medium to be described later. Oxide, carbonate, oxalate, sulfate, hydroxide, etc. Some of these compounds may be used alone or in combination, and the reactivity between the raw materials and the raw materials may be high after the firing without leaving impurities. The best thing is to make Magnesium hydroxide is used. When it is easy to mix evenly, it is preferable that the desired physical properties of the magnesium compound are below the average diameter, especially 0.2~ as a wrong compound, which is used as a dispersion medium to be described later. It is insoluble or insoluble. From the & 乍, it is possible to use, for example, oxidized & oxidized acid salts, nitrates, hydroxides, organic acid salts, etc. These compounds can be used for free. Species or more than two. Even among these, it is preferable to use yttrium oxide in the aspect of low volatility and inability to be solved by 201229210. From the viewpoint of uniform mixing, it can be ~ a ^ If you look at it, it is best to use the compound of the compound a! The 千 system has a thousand-average particle size of 50//Π1 or less, especially 疋丄~d 0 # m 〇 as a violent compound system, and, for example, manganese Oxide, hydroxide, sulphate, nitrate, il salt, organic acid salt, etc. This compound can make 帛1 or 2 _ °%, .^ . c even in these cases, After firing, there is no residual impurity and In view of the fact that the solid is soluble in the matrix of the mother, it is preferred that the carbonated compound can be water-soluble or water-insoluble. In the state where the manganese is not water, the homogeneous mixture can be mixed. When the central county ^ _ is seen, the average particle size is preferably ΙΟμιη or less, especially 1 to 9//m. As an additive element, it is used for the private &&& The dispersing medium is insoluble or insoluble. For example, a series of compound compounds added as a compound includes, for example, a gas, a cerium, a cerium carbonate, a nitrate, an organic acid salt, or the like. ^ One or two records can be used for the σ system. From the viewpoint that it is easy to mix the sentences uniformly (4), the ideal physical property of the compound: the average particle diameter is the heart, and is usually 1 to 9 y m.荷,Γ: The gasification town, magnesium compound, wrong compound, violent compound, and the manufacturing history of the compound containing hexahydrate, which is added for the purpose, but 'for the purpose of manufacturing the purity of the method The phthalate phosphor, therefore, is intended to reduce the amount of impurities as much as possible. In the present production method, the mixing ratio of the gasification cake to remove the magnesium, the magnesium compound, the bismuth compound, the manganeseated 201229210 compound, and the compound containing the additive element added due to the church y can be combined with the manganese required The composition of the phthalate phosphor is activated to appropriately select the ratio of the raw materials. Specifically, X.·* Λ In the state in which the compound containing an additive element is not added, the mixing ratio of the fluoroantimony magnesium compound, the cerium compound, and the manganese compound is the number of molecules of the magnesium hydride which is added to the fluorinated town. 6〜3。 The 莫 5 孝 孝 孝 孝 孝 孝 孝 孝 孝 孝 孝 孝 孝 孝 孝 孝 孝 孝 。 。 。 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 。 。 Further, the addition amount of the singulated 5 substance is a ratio of the number of magnesium atoms in the magnesium compound to the molar ratio (Mg/(Ge+ Μη)) of the total number of atoms of the ruthenium atom in the ruthenium compound and the violent atom in the stilbene compound. More than 〇, less than 4, preferably 3.4. The amount of the compound added is the molar atomic number in the compound, and the total number of atoms in the bismuth atom and the manganese atom in the bismuth 5 The ratio (Mn/(Ge+ Μη)) becomes 0. 001~0· 〇5, preferably 0.005 〇.〇3. Further, 'the table is good in the state in which the compound containing the Μ1 element is added, and the number of M1 atoms in the compound containing the M1 element is relative to the total number of atoms of the magnesium atom in the magnesium compound and the M1 atom in the compound containing the M1 element. The Mohr number ratio (Ml/Mg+M1) is greater than 0, less than 0.2, preferably 疋 is greater than 0, less than 〇·15, and the Μ2-containing compound is added in the state of adding the M2-containing element S containing the M2 element. The molar ratio (M2/Ge+M2) of the total number of atoms of the atomic number to the atomic number of the M2 atom in the compound containing the M2 element is greater than 〇, less than 〇. 28, preferably More than 〇, less than 0.25. 201229210 Fluoride town # compound, wrong compound, violent compound, and added element compound added as needed, mixed with a dispersing medium to form a mixture 2 as a dispersing medium. It is preferred to use water or a water-soluble organic solvent to practice 2 in water. And the composition of the aqueous solution. From the viewpoint of efficiently performing mixing using a medium dry mill, the concentration is 5 to 4% by weight, and the solid content of the most mixed liquid is more preferably / preferably 10 to 30% by weight. The method in which m is used to prepare a mixed-mixed polymer is a treatment of a medium dry mill of a machine which is pulverized and mixed while the manufacturer m2 is (4). It is possible to more easily obtain a uniformly mixed slurry which is uniformly mixed in the manner of each raw material. As a media mill, it is possible to vibrate crying & pellet mills, ball mills, m °, sand mills, etc. It is especially preferable to use a granule rolling mill. In its state, the operating conditions or the use of a pulverizing mill to match the size or location of the device, "type and size" are optional. If it is used in a more efficient manner, the material can be used in a more efficient manner. (1) 』In the mixed slurry, the agent can be blended with the dispersant. Dispersant. When the dispersion is in the state of water, select the appropriate one for the class. In the dispersing agent, for example, 彳乍 is a dispersing agent, such as 俅田々剂, polyacid sulfate salt, and the like. From the viewpoint of obtaining a sufficient interfacial activity of a total of eight μ, it is preferably a dispersant in a mixed polymer; and from the viewpoint of 3 political effects, particularly, 0.1 to 5 wt%. The concentration is 0.01~10 by weight. From the point of view of the so-called material _^°° (4), if it is sharp point, it will hang in the south luminescence efficiency.

S 201229210 The average particle size of the solid component is hereinafter, preferably... the following is particularly preferably 〇. 1~〇. 5 " m. The average particle diameter can be measured by a light scattering type particle size distribution measuring apparatus. 9 ^ The slurry obtained in this way is uniformly mixed, and is attached to the jet of (B) to pass the _ reaction precursor. In the mixed solution: the mouth: a method other than the drying method, but in the present manufacturing method, the drying method is employed in the following: In detail, when using the spray drying method, the dragon is used to obtain a true ball or a reaction precursor similar to the shape of the true ball. Since A ' can easily obtain spherical manganese: strontium salt phosphor particles . Further, when the blast drying method is used, the composition of the reaction precursor is obtained by the firing of the precursor particles in a state in which the raw material particles of the solid component are densely clogged. a ... In the spray drying method, the mixed liquid is atomized by a predetermined means, and the fine precursor is produced by drying to obtain a reaction precursor. The atomization of the mixed solution is, for example, a method of using a rotating disk and a method of using a pressure spray. In this process, any method can also be used. In the spray drying method, if the powder is sufficiently dried to be stably dried, it is preferably dried at a drying temperature of 100 to 2, particularly preferably 15 to 25 (r. 4 in the spray drying method). The relationship between the droplet size of the atomized mixture and the size of the raw material particles of the dimorphic component is affected by the stability of the stability of the mixture, and the effect of the precursors on the reaction. In detail, the size of the raw material particles of the two-state component is relative to When the droplet size is too small, the solid 11 201229210 drops become unstable, and π~ each is easy to dry and dry. ± If you look at it, then the last b is reversed. From this point of view (1) is good The solid state in the mixed liquid becomes the aforementioned range 1 particle size ", especially 1 〇 ~ small 5~15 〇 liquid is supplied to the spray dry fresh (4). It is good to consider the viewpoint and decide the supply of the 耵钇 耵钇 耵钇 盗 盗As a result of the chain activation of the target, the particle size control of the suspension cups is better. The average particle size of the spray drying method is A. m #好是1~3〇", special best list The average particle diameter is determined by, for example, a light-scattering particle size measuring device. The spherical reaction precursor obtained as a sample is added to the firing process to obtain a dragon activation. The broth acid salt camp body. It is best in the system. The method 'ideal is above mot, the firing is added to the spray: the precursor is obtained. In addition, the so-called dissolution begins and cannot be dimensioned; 'Therefore, the upper limit temperature of the firing temperature is 1 250... In addition, when the firing is performed at 1 050 to 12 〇〇t, a single target composition can be obtained while maintaining the shape of the particles. The surface can be made smoother. In other words, it is particularly desirable from the viewpoint of obtaining high luminous efficiency. In the present manufacturing method, the firing time is not critical. Generally, if it is firing For 3 hours or more, particularly 5 to 36 hours, a manganese-activated strontium silicate phosphor which should be satisfied can be obtained. In the present production method, the atmosphere of the firing is not critical, and for example, it can be an oxidizing property such as the atmosphere. gas _ And in any atmosphere of an inert gas atmosphere

S 12 201229210 One. A firing system such as & can be attached to the firing process as needed. It is possible to carry out the pulverization treatment or the pulverization treatment for the manganese-activated decanoate glomerium obtained after the calcination, and also perform the sub- <amp; The acid salt of the dysprosate as the ideal property of the phosphoric acid phosphor is the average particle obtained by the rhythm particle size distribution measuring device (4) 5~心好疋10~30#ιη〇 Can be 1:2 y rk τ Jay · Hunting from the average particle size to the above range and the efficiency is better to absorb the vines also x first. The average particle size was measured by a laser diffraction/scattering particle size division and a knife cloth measuring device (LA-920) manufactured by Horiba. The BET specific surface area system 〇 τ 2 / bar system 0.1~h2/g, preferably 〇.2~〇7m / g. The excitation light can be sufficiently absorbed by the BET specific surface area into a rabbit's range, and the order of w and red 以 can be prevented to prevent the purity of the excitation light, iUt, and the luminescence intensity can be sufficiently increased. In addition, the particle shape is spherical in the form of a globular L-cured fluorescens by the method of the present manufacturing method. In addition, the so-called particle shape is a spherical shape as long as it is a spherical shape. "Shape" does not necessarily need to be a real ball. In the case of the degree of spherical sound, ♦ y and sphericity, the manganese activated strontium silicate fluorescent system has a spherical opening, and the degree can be 1.0 to L8, especially 疋1. 0~1. 7 The spherical shape of private. The ^ is a spherical manganese-activated strontium hydride. It also makes the quantum yield better. The luminous intensity also becomes higher. It is defined by the real area of the true circular area/projection pattern formed by the maximum diameter of the technical pattern of the film 2012 20121010. Therefore, the closer the value of the sphericity is to 1, the closer the particle is. In addition, the surface of the particles of the manganese-activated decanoate fluorite obtained by the present production method is preferably smooth. The smoothness of the surface of the particles of the activated agglomerated mortar is, for example, When the particle size is expressed by the degree of concavity and convexity, the particle system of the present invention may have a degree of concavity and convexity of 1·G to 1.8, particularly 1. 〇1.5 degree of smoothness. When the straw is calculated from the length around the projected figure The true area of the circle/the real area of the projected figure is defined. Therefore, the surface of the particle is more smoothly smoothed. The value of the unevenness is closer to the true sphericity and the degree of unevenness of the image of the month _j, for example, an image analysis device can be used. As an example of such a device, LUZEX AP manufactured by nic〇le Co., Ltd., etc. is used. The measurement is carried out by randomly extracting three particles, and the magnification of the particles is matched with the size. Further, it is 4 to 300,000 times. The manganese-activated yanoate fluorescent system of the present invention can be surface-treated by the metal oxide for the purpose of improving moisture resistance. The metal oxide is used, for example, by Be, Mg, A丨, si,

Dy, Ho, Er, Tm, Yb, Lu, Th, Pa

One s 14 201229210 or two or more metal oxides selected from I 〇u , Ba, La, Hf, pm, Sm, Eu, Gd, Tb, Pa, U, and Pu. As a method of coating the surface of the particles of the manganese-activated strontium silicate phosphor particles by these metal oxides, a conventional method can be used, and if an example is shown, the use of the aforementioned metal elements is exemplified. a metal alkoxide, adding the aforementioned metal alkoxide to a slurry or suspension containing the manganese activated strontium silicate phosphor particles, and if necessary, performing the metal in the presence of an acid catalyst or an ia catalyst The hydrolysis reaction of the alkoxide, a method of uniformly surface-treating the surface of the particles of the manganese-activated yanosilicate phosphor particles by the metal oxide just described. The manganese-activated phthalate fluorescent system obtained in this manner can be suitably used as a red phosphor, and the red camping system can be used for, for example, a display device such as an electrolysis display, a plasma display, or an electroluminescence. Various: the use of light l #. Further, since it has the excitation light f close to 45 Gnm, it can be applied to the blue LED excitation phosphor. Special: 疋 It is suitable for the display components of electric excitation light. In addition, it is also possible to use the method of exciting the green glory in blue, and to use the blue LED element and the blue color to excite the green phosphor, or to use the blue 711 piece and the blue color to illuminate the yellow illuminating Light body is used to apply to white LEDs. [Examples] The present invention will be described by way of examples under X. However, the scope of the present invention is not intended to be a simplification of the present invention. There is no special restriction. "% indicates "% by weight". [Example 1] 15 201229210 (A) Uniform mixing slurry preparation process: Scale magnesium hydroxide (average particle size 0.57 # m), magnesium fluoride (average particle size 19. 〇 / " m), oxidation锗 (average particle size of 17.7/ζπΟ and manganese carbonate (average particle size 5.2#m) such that the molar ratio of Mg: Ge: F: Mn becomes 4 0·99· 2.0. 〇·〇ι, ie Mn / (Ge+Mn) = 〇.〇1, MgF2 / (Ge+Mn) s^Mg/ (Ge+Mn) = 4.0' is charged to the ball mill. Add water and dispersant to the ball mill (Kao) Preparation, Poise (P〇ise): 21〇〇), to prepare a mixture of solid concentration ι5%. The concentration of dispersant is 2%. In the ball mill, zirconia balls with a diameter of 〇 _ 5mm are placed and wetted. The mixture is pulverized by the method for 2 hours. When the average particle size of the solid component of the slurry after mixing and pulverization is measured by the light scattering method, it becomes 〇3. (B) Spray drying process (drying process) : Then 'the temperature at the inlet is set at 2 〇 (the jet dryer of rc, the supply liquid is supplied at a supply rate of 45 ml/min to obtain the reaction precursor. The average of the reaction precursors) The diameter system is 22. 8 // m. The electron micrograph of the reaction precursor (SEM image) is shown in Figure 1 ( &) and Figure 1 (b). (C) Firing process: The reaction precursor is loaded into The electric furnace is fired in the state of 丨15〇〇c in the atmosphere for 6 hours. The manganese activated 锗 of 3Mg〇·MgF2 · 0. 99Ge〇2 : 0_ OIMn is obtained for this purpose. An alkanoate. When the X-ray diffraction measurement was performed on the obtained manganese-activated strontium silicate phosphor, it was confirmed that the manganese-activated strontium silicate fluorescent system was composed of MgMGe5〇24 and MgO, and became a single 201229210. A composition of manganese activated strontium hydride phosphor. The SEM image of the manganese activated strontium silicate phosphor is shown in Figure 2 (a) and Figure 2 (b). [Example 2] In the first embodiment, the slurry preparation process was carried out, and the molar ratio was Mn/(Ge+ Μη) = 〇· 〇〇5, and the others were the same as in Example 1 to obtain 3Mg0 · MgF2. 0. 995Ge〇2 : 〇. 〇〇5Μη4 + manganese activated strontium hydride phosphor. X-ray is obtained in the obtained manganese activated strontium hydride phosphor At the time of the measurement, it was confirmed that Mgi4Ge5〇24 and Mg〇 constituted a manganese activated strontium hydride phosphor which became a single composition. [Example 3] In addition to the uniform mixing slurry preparation in Example 1 (a) In the process, the molar ratio is Mn/(Ge+ Μη) = 〇·03, and the others are the same as in Example 1 to obtain 3Mg0·MgF” 〇.97Ge〇2: 〇〇3 core 4+ manganese Activate the phthalate phosphor. When the X-ray diffraction measurement was performed on the obtained manganese-activated strontium hydride phosphor, it was confirmed that Mn-activated yanoate fluorite consisting of ruthenium 14 at 5 〇 24 and 〇 as a single composition. body. [Example 4] The same procedure as in Example 1 was carried out except that the slurry preparation process was uniformly mixed in Example 1 and the molar ratio was MgF2/(Ge+Mn) = G.6. 3. 4MgG · G. 6MgF2 · G. 99Ge〇2 : Mn.〇1Μη4+ manganese activated strontium hydride phosphor. When the manganese-activated strontium sulphate phosphor was obtained for the enthalpy ray diffraction measurement, it was confirmed

Mg"Ge5〇24#n Mg0 is composed of a manganese-activated strontanoate phosphor which is a single composition. 17 201229210 [Example 5] Except that in the (a) homogeneous mixed slurry preparation process of Example 1, the molar ratio was MgF2〆(Ge+Μη)=3.0, and the rest was the same as in Example 1. A pulverized activated tyrosine phosphor which is MgO · 3MgF2 · 0. 99Ge〇2 : 0. 0lMn4 + is obtained. When the X-ray diffraction measurement was carried out on the obtained activated strontium sulphate phosphor, it was confirmed that the manganese-activated strontium hydride phosphor which was composed of MgHGe 5 〇 24 and Mg ’ became a single composition. [Example 6] The same procedure as in Example 1 was carried out except that the slurry preparation process was uniformly mixed in Example 1 and the molar ratio was Mg/(Ge + Μη) = 3.0. 2Mg0·MgF2· 0.99Ge〇2 : Ο.ΟΙΜη" The activated strontium sulphate phosphor. When X-ray diffraction was measured on the activated strontium sulphate phosphor, it was confirmed by MgHGes 〇24 and Mg〇 constitute a manganese-activated yanoate phosphor of a single composition. [Example 7] Except for the (C) firing process of Example 1, the firing temperature was 1〇75 c The same is the same as in Example i to obtain a manganese-activated yanoate phosphor which is 3Mg〇·heart^·〇.99Ge〇2: 0.01Mn4+. The manganese-activated decanoate phosphor obtained in the same manner. On the other hand, in the X-ray diffraction measurement, a manganese-activated strontium sulphate phosphor composed of a ruthenium 5 〇 24 and Mg 确认 was confirmed to be a mono-composition. [Comparative Example 1] Except in the example [ B) Spray drying process (drying process), in order to replace the use of jet dryer to obtain spherical particles, so, still straight 2 01229210 Other than the ground static and dry wet pulverized slurry, the other phase 1 is obtained as 3Mg〇 · MgF2 · 0. 99Ge〇2: 0. 01Mn4 +

Look at the salt camp. At the time of the obtained manganese-activated decanoate X-ray diffraction measurement, a manganese-activated yanoate phosphor having a single composition of MguGe5〇24 and MgO was confirmed. The SEM of the manganese-activated decanoate phosphor is shown in Fig. 3 3 (b)' to form a composition (a) and an image by vigorously activating the steroid in the examples. 19 201229210 Π<] firing process firing temperature CC) 1150 1150 1150 1150 1150 1150 1075 1150 Drying process 1 away, entanglement; CO (# m) 〇〇CO CS3 C3 LO 〇〇〇〇CN1 CO 々· 03 οα CC CN1 CO CN3 (ΝΪ T—< co 03 CO <〇 drying method spray drying method spray drying method spray drying method spray drying method spray drying method spray drying method spray drying method static drying method mixture preparation process u solid component The average particle i B Ο CO ο CNI CO 〇CD CO CD CNI CO Ο) CO CO 〇 CO CO 〇) LO CO 〇CNJ CO 〇 mixing method wet granule rolling mill wet granule mill wet granule rolling Mill Wet Particle Rolling Mill Wet Particle Rolling Mill Wet Particle Rolling Mill Wet Particle Rolling Mill Wet Particle Rolling Mill i Raw Material Loading (Mohr Number Ratio) Mg/(Ge+Mn) Inch CO MgF2/(Ge+Mn) 〇〇Τ-Η CD CO 〇〇CO 〇〇1—Η ◦ Mn Mn/(Ge+Mn) 1 1 〇〇0. 005 CO ο <=>〇< =) Τ - < 〇〇 1 - < 〇 c = > 1 - ^ 〇 CD CD 实施 Example 1 Example 2 Example 3 Implementation Example 54 Example 6 Example 7 Comparative Example 1.哒f®w-&-ll鲧》趣穷条 Left ^馁颦趔资^嗖3食<««)矽茛€(026丨3)鲥铋奴. Back to wwwvg( 026丨π ) 鲥铋铋茛 Φ 衂 & ΊΙ粲 ΊΙ粲 某 某 某 某 某 某 友 友 友 友 友 友 友 友 友 友 友 友 友 友 友 友 ff ff ff ff ff ff ff ff ( ( ( ( ( ( (

S 201229210 [Physical property evaluation] The average particle diameter, true sphericity, unevenness, and BET specific surface area of the stimuli-activated tyrosine phosphor obtained in the examples and the comparative examples were measured by the methods described above. Further, the surface of the particles of the activated agglomerate phosphor particles was observed at 3,000 times SEM observation. These results are shown in Table 2. [Table 2] Average particle diameter (//m) Sphericality and convexity BET specific surface area (mVg) - State of secondary particles Example 1 20. 5 1. 04 1. 32 0. 24 Formation by agglomeration of primary particles Sphere. Example 2 21.2 1. 03 1.31 0. 23 // Example 3 21. 0 1. 01 1. 32 0. 24 // Example 4 20. 8 1. 02 1. 33 0.24 实施 Example 5 22. 5 1. 04 1. 32 0. 26 // Example 6 20. 2 1. 05 1. 32 0. 23 实施 Example 7 21. 6 1. 04 1. 31 0. 58 〃 Comparative Example 1 9. 27 1 75 1.90 16.22 Amorphous [Evaluation] For the manganese-activated yanoate phosphors obtained in the examples and comparative examples, the internal quantum efficiency at an excitation wavelength of 45 〇 nm was measured by the following method. And relative luminous intensity. These results are shown in Table 3 below. [Internal quantum efficiency] Using a fluorescent spectrophotometer (F-7 〇〇〇) manufactured by HitachiShang Technology Co., Ltd. and an attached integrating sphere, the excitation light is 45 〇 nm, and the scanning starts from 42 至 to 70 〇 nm. Find the conversion efficiency. Further, alumina powder was used in the type 5 material for measuring the total scattered light. The spectral intensity integral value 'from the beginning of 2012 201210 to 475 nm obtained by alumina is used as the amount of excitation light, and the integral value of the spectral intensity from 435 to 475 nm obtained by the phosphor sample is taken as the amount of excitation light after absorption. The spectral intensity integral value 'from 6 〇〇 to 70 〇 nm obtained by the phosphor sample was obtained as the amount of fluorescence. The internal quantum efficiency is obtained by the following formula. Internal quantum efficiency (%) = 1 〇〇 X amount of fluorescence + (excitation amount - amount of excitation light after absorption). [Relative luminous intensity] A fluorescent spectrophotometer (F-??) manufactured by Hitachi High-Technologies Co., Ltd. was used to obtain excitation light of 450 nm, and scanning was performed from 47 Å to 8 〇〇 nm to obtain a fluorescence spectrum. From the obtained intensity values, the relative luminous intensity was obtained by taking the maximum luminous intensity as 100. [Table 3] Internal quantum efficiency (%) Relative luminous intensity Example 1 100 Example 2 ^_iL2 94. 6 Example 3 55. 2 70. 〇 Example 4 73. 6 Example 5 68. 6 Example 6 70.2 Example 7 105.3 79. 3 Comparative Example 1 48. 1 and FIG. 3 are clearly and clearly judged: the manganese-activated strontanoate strontium phthalate phosphor of Example 1 (the present invention) The ball is formed by agglomeration of primary particles more than the manganese activation of Comparative Example 1.

S 22 201229210 shape. The decanoate fluorescent system of Comparative Example 1 became an amorphous shape. Further, it was confirmed from the results shown in Table 3 that the vigorously activated strontium sulphate phosphor of the first embodiment (the present invention) was compared with the manganese activated strontium silicate phosphor of Comparative Example 1, The luminous intensity in the red region is made higher. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (a) and Fig. i (b) are SEM images of the reaction precursor obtained in Example J, Fig. (a) The magnification is 1〇〇〇, Figure i (the magnification is 3000 times. The manganese activation 锗2 (a) obtained in Example 1 is 1〇〇〇 times, Figure 2 (a) and Figure 2 (b) The sem image of the k-salt phosphor particles in the example, Figure 2 < Figure 2 (b) is 3000 times the magnification. The manganese activated 锗3 (a) obtained in Example 1 is 1 〇〇〇 times, 3 (a) and Fig. 3 (b) are SEM images of the alkanoate phosphor particles of the comparative example, Fig. 3 < Fig. 3 (b) is a magnification of 3 。. [Main component symbol description] twenty three

Claims (1)

201229210 VII. Patent application scope: 1 · A method for producing manganese activated strontium silicate phosphors by the following general formula (1): a ( Mgi-xMlx) 0 · bMgFi · c ----- -- Vi; (In the chemical formula, 'MH system means i or two or more elements selected from the group consisting of Zn, CU, Cd, Ca, Hg, and SrBa, and M2 means a group consisting of ^, Sn, and pb. The group selected or the two or more elements, a indicates 〇&lt;a$4'b indicates 〇.5$b$4'c indicates 〇8&lt; 0 = c ^ 1. 2 5 η Table <No 〇〇 ... ... χ χ χ χ χ χ χ χ χ χ 2 2 2 2 2 2 2 S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S One or two or more kinds of the compound containing an element of a fluorinated town, a compound other than magnesium fluoride, a wrong compound, == (a) element added as needed, and a _ element element, and are deducted from the dispersion medium. For the raw material mixture, the body is mixed with the powder, and the precursor is mixed with the "., ·, formula", and becomes the reaction precursor, and the reaction is fired. In the flat manufacturing method, the manganese-activated strontium sulphate fluorescence average particle size of the first item is determined to be i, and the reaction precursor is used to make the reaction precursor horse 1 to 5 〇 &quot; m. ° The manufacturing method of the 3rd carcass of the patent range of the month is the following. The 1 or 2 item of the activated agglomerate phosphoric acid diameter is below. ', the average particle of the solid component of the mixed slurry of the homogenate S 24 201229210 4. If applying The method for producing a manganese-activated yanoate phosphor according to any one of the items 1 to 3, wherein the firing temperature is 1 000 ° C or higher.