TW201202394A - PROCESS FOR PRODUCTION OF Eu-ACTIVATED ALKALINE EARTH METAL SILICATE PHOSPHOR - Google Patents

Abstract

Provided is a process for the production of an Eu-activated alkaline earth metal silicate phosphor wherein the ratio of the total number of constituent metal atoms (Sr, Ba, Eu, Si) to the number of constituent Si atoms is 4 : 1 or 3 : 1. According to the process, a precursor having a uniform chemical composition can be synthesized at a lower temperature than that of a conventional process, and a single-phase Eu-activated alkaline earth metal silicate phosphor that has a uniform chemical composition and exhibits high luminance can be efficiently produced at a low cost by heat-treating the precursor. A process for the production of an Eu-activated alkaline earth metal silicate phosphor, characterized by including a step (1) of preparing aqueous solutions that contain the constituent metal components, namely, strontium, barium, europium, and silicon respectively, mixing the aqueous solutions together, and keeping the resulting mixture at a solution temperature of 30 to 100 DEG C to form a transparent gel wherein all the metal components are dispersed uniformly and completely.

Description

201202394 VI. Description of the Invention: [Technical Field] The present invention relates to a uranium-based phosphor that emits Eu2+ by high-brightness yellow luminescence by excitation of ultraviolet light to a visible region (turtle) Form (Sq-y, Euy) 3si〇5 (where ' 〇&lt;y&lt;〇.i)); and exhibiting high-brightness green to yellow luminescence by excitation of ultraviolet light to the visible region (Bax, SrmEiiyhSiOsC, where 〇&lt;x<dark&lt;y&lt;〇.l), composition formula (Bax'Srn-y, Euy)2Si〇4 (where 〇&lt;x&lt;l,0&lt;y&lt; 0.l) A method for producing an Eucalcium-activated alkaline earth metal silicate-based phosphor. [Prior Art] A white light emitting diode (LED) is a liquid crystal display (LCD) that combines the light of a near-ultraviolet to blue light-emitting LED and a phosphor to produce white light. , liquid crystal display) is actively developed, and the development of lighting applications continues to advance as the next generation of applications. As the white LED phosphor used in the white LED, YAG: Ce3+ which exhibits yellow fluorescence by blue excitation or green to yellow fluorescence (Ba, Sr, Ca) has been known. 2Si〇4: Eu2+, sr3Si〇5: Eu2+, etc., but a phosphor of higher brightness is desired. In general, a method of synthesizing a phosphor is, for example, as disclosed in Non-Patent Document 1. The raw material powders are mixed in a wet or dry manner, placed in a sinter barn, and calcined and heated at a local temperature, and combined with a solid phase reaction between the raw materials to form 100118260 201202394.

The purity of the crystal phase is extracted and the Eu2+ homologue as an activator is dispersed in the parent crucible. As described in Patent Document 2, a metal oxide is produced by a solid phase method.

If the degree of calcination or elongation is increased, the sintering is improved and the particle size is increased. Therefore, the glittering burr which pulverizes the sinter to reduce the particle size causes damage due to pulverization, and causes a problem that the luminescent intensity is lowered. As a countermeasure for lowering the calcination temperature or reducing the particle size, the liquid phase method for synthesizing a metal oxide is carried out by using a liquid phase to prepare a body before the metal oxide and calcining the precursor. the study. In the liquid phase method, the metal element is dissolved and mixed in the solvent, so that uniform mixing at the atomic level can be performed, and it is not necessary to cause solid phase diffusion of the oxide raw material powder as in the solid phase method, so that synthesis at a low temperature can be expected . Further, by low-temperature synthesis, an increase in crystal grain size can also be suppressed. 100118260 201202394 As an example of such a liquid phase method, there is a precipitation method disclosed in Patent Document 1. In Patent Document 1, a precipitate is formed from a metal salt and TEOS (tetraethoxysilane) or tantalum, and a phosphor is synthesized by drying and heat treatment. The metal salt and TEOS do not form a precipitate at the same time, but the powder material is brought into a state of being more refined, and there is a problem that it is not uniformly mixed on the elemental level. Further, in Patent Document 2, as a liquid phase method, a citric acid method, a coprecipitation method, a metal alkoxide method (sol-gel method), a thermal decomposition method, a complex polymerization method, and a PVA method are described. The method of synthesizing a hydrothermally oxidized material to produce a front weft is described, and a comparison of the materials is described, and a hydrothermal gelation method is used, whereby the metal oxide phosphor can be efficiently synthesized. According to Patent Document 2, if the water is mixed with the water, the metal element is dispersed, and the gel is dried and heat-treated. Thereby, the lying body can be obtained. Since the gel utilizes te〇s, it has a feature of less organic matter. By hydrothermal gelation of a liquid phase mixed with atomic level a, it is possible to produce a uniform metal with a short chemical composition, and (4) a composite metal having a uniform chemical composition by the heat of (4)^ Force, so the secret gold is divided into the four (4) when the ratio is small, there is a problem that can not make all the gold, and the gel. The composition is contained in 100118260 201202394. In the case of the liquid phase method other than the hydrothermal gelation method, the body of the soil-based metal silicate is used in the case of the body of the phosphor, and TEOW is also used. Oxide. It is prepared by compounding a metal salt with TE〇S, and dissolving and mixing them in a suitable solvent to prepare a uniform gel. When a non-aqueous solvent is used as a solvent, a homogeneous mixture can be obtained. However, if water is used as a solvent, the tetraethoxylate is hydrophobic, so that the reaction between TEOS and water is partially hydrolyzed, and a local reaction is caused. Possibility, while there is a problem with obtaining (four) mixtures. On the other hand, there are also non-aqueous solvents, especially I +, , /, 疋 organic solvents, which are harmful to the human body or fire. However, in recent years, it has been disclosed as a water-soluble compound (wss, SQluble Silic), which is replaced by pmpylene glycoxy, as a water-soluble compound. The four ethoxy groups, because they contain (4), can be stably present in the acidic aqueous solution of the vessel. The aqueous solution of the aqueous solution of the mixture is subjected to hydrolysis and polycondensation by heating or the like to obtain a SiQ2 gel. The water-soluble cerium yttrium has a gelation ability larger than TE〇s. Non-Patent Document 2 discloses that a water-soluble cerium compound and a metal zinc raw material aqueous solution are mixed and hydrothermally processed. The precursor is calcined in a reducing gas atmosphere to obtain a ΜηθΚ4 phosphor which is added with Μη. The ratio of the metal element of the fluorescent system (the sum of Zn and Si) to Si is 3:1, in the case of TEOS, Gelation of all-metal components is difficult, but by using 100118260 201202394 water-soluble cerium compound, it is possible to produce a gel containing all-metal components. However, since the hydrothermal synthesis method must be used for the preparation of the precursor, there is a problem that heat treatment must be performed in a pressure vessel such as a high pressure dad. In this case, the inventors of the present invention have tried to produce a metal component element and a si by using a hydrothermal gelation method using a water-soluble shixi compound.

The ratio of (Sri-y, Euy) 3Si〇5 phosphor, (Bax'Sq-x-y'EuyhSiCV and the ratio of metal component to Si is 3: ii (Bax, Sri_x_y EUy) 2Si〇 4 The phosphor of Eu activates the lithium silicate phosphor precursor. As a result, it is found that it is difficult to make the whole metal component uniform and all contained in the gel, and it is easy to cause composition deviation or uneven distribution of elements. [Technical Documents] [Patent Document] Patent Document 1: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2008-007390. Non-Patent Document 1: "Fluorescent Handbook", Ohmsha Corporation, P. 166 Non-Patent Document 2 '· N. Takahashi, Y. Suzuki, M. Kakihana, &quot;Synthesis of Zn2Si04 : Mn2+ green emission phosphor by hydrothermal gelation Method using a novel water soluble silicon compound&quot;, Jounal of the Ceramic Society of Japan, 2009, vol. 117, No. 3, p. 313-315 100118260 7 201202394 [Disclosure] (Problems to be solved by the invention) The present invention The purpose is to mention Provided by a manufacturing method which is capable of eliminating the above-mentioned various technical problems when manufacturing Eu-activated alkaline earth metal silicate phosphors as described below, and capable of synthesizing the chemical composition with higher homogeneity than the previous method, and The precursor body is subjected to heat treatment, thereby efficiently and inexpensively producing a high-intensity soil-based metal-based phosphoric acid phosphor having a uniform chemical composition and a single phase. The Eu-activated alkaline earth metal phthalate fluorescent system composition formula (Sri y, Euy) 3Si〇5 (where ' 〇 &lt;y&lt;〇.i), composition formula (Bax, Sri x yEUy) 3Si〇5 (where ' 0&lt;χ&lt;1,〇&lt;y&lt;(U ), and the ratio of all metal component elements (Sr, Ba, Eu, Si) to Si is 4:1; composition formula (Bax'Srh-y'EuyhSiC^ (where ' 0&lt;x <卜0&lt;y&lt;01 ), and the ratio of total metal component elements (Ba, heart, Eu, Si) to Si is 3: 1. (Means for solving the problem)

The present inventors have made an effort to solve the above problems, and as a result, have obtained the following findings, and have completed the present invention: a composition formula of self-constitution (Sri-y, Euy) 3Si05 (which is ^1) (Baj^Sri-ry, E\iy)3Si〇5 (where 〇&lt; X (1 ' 〇&lt;y&lt;〇1), composition formula (Bax, Sr Bux_y, EUy) 2Si04 (where 〇&lt;&lt;1 〇&lt;y&lt;c〇.l) is selected from the group consisting of alkaline earth metal silicate phosphors, which are formed into a knife, and the whole metal components of steel, bismuth, pin, and shixi are made into an aqueous solution, and the force is mixed. 'Keep in the liquid temperature of 3G~, thereby forming a gel in which the whole metal is uniformly distributed in 77'. Then, the chemical composition is obtained by drying the lyotropic rubber, heat treatment in the atmosphere of 100118260 201202394, and heat treatment in a reducing gas atmosphere. An alkaline earth metal silicate phosphor which is uniform and consists of a single phase crystal phase. The first invention of the present invention is a method for producing an Eu-activated alkaline earth metal silicate phosphor, which is a self-composition (Sri-y, Euy) 3Si05 (where 0 &lt; y &lt; 0.1), composition formula (BawSh-rpEiiyhSKM where 0 &lt; χ &lt; α, 0 &lt;丫&lt;0.1), composition formula (6 & heart 81:1-}1-7, ugly 1^) 281〇4 (where, 0 &lt; meaning &lt;1,0 &lt;y&lt; 0.1) A method for producing a Eu-activated alkaline earth metal silicate phosphor, comprising the following step 1: [Step 1] preparing an aqueous solution of each of the element materials of ruthenium, osmium, iridium, and osmium which constitute a metal component, A step of maintaining a liquid temperature of 30 to 100 ° C in a mixed aqueous solution of the aqueous solution prepared by mixing to form a gel in a state in which the total amount of all metal components is uniformly dispersed. The second invention of the present invention is an Eu-activated solution. A method for producing an alkaline earth metal silicate phosphor, which is a self-composition formula (Sri-pEuyhSiOK, 0 &lt; y &lt; 0.1), and a composition formula (6 pressure \, 81: 1-5 ^, £%) 38105 (Where, 0 &lt; 乂 &lt; 1 , 0 &lt; 7 &lt; 0.1), composition formula (ugly. 81 * 1-3 ^, ugly 1 ^) 281 〇 4 (where 0 &lt; again &lt; 1 , 0; A method for producing an Eu-alkaline earth metal silicate phosphor selected from the group of y &lt; 0.1), which comprises the following steps 1 to 4: [Step 1] 100118260 9 201202394 Production as a constituent metal component The aqueous solution of each of the raw materials of each of the elements of the 钡, 录, and the shixi is kept at a liquid temperature of 30 to 10 Ωt by mixing the aqueous solution of the aqueous solution prepared by mixing, thereby forming a gel in a state in which the total amount of the total metal components is uniformly dispersed. [Step 2] a step of drying the gel formed by the step 1 to form a dried product, and removing the solvent contained therein; [Step 3] Circulating the above-mentioned money of the step 2 t to the atmosphere a step of obtaining a calcined powder by heat treatment to remove the organic matter; [Step 4], performing a heat treatment of the calcined powder formed in the step 3 in a reducing gas atmosphere to obtain a fluorescent test. According to a third aspect of the present invention, there is provided a method for producing a Eu-activated soil-based metal (IV) salt phosphor according to the first aspect or the second aspect of the invention, wherein the mixed aqueous solution in the step is used as a constituent metal component _, a ship The concentration is set to i ~ 5.5 mol / L. The invention of the jujube ... the praise or the second invention of the Eu activating, the method of manufacturing the sputum sulphate sb. The aqueous solution of Zhongshi Shixi is an aqueous solution obtained by adding propylene glycol to tetramethoxy Wei and heating, mixing and mixing. The fifth invention of the present invention is a living earth-like metal according to the second invention. 118260 100118260 201202394 A method for producing a salt glaze, wherein t is included after step 3, by classification from the above Step 3 t The step of forming the pre-sintered material to remove the coarse particles above the contact. (Effect of the Invention) According to the present invention, when the Eu-activated soil-like metal silicate phosphor is produced as follows, the body can be lying higher than the previous method with a lower degree of homogeneity, and the precursor is By heat treatment, a uniform and single-phase high-brightness Eu-enriched alkaline earth metal silicate phosphor can be efficiently produced, and the Eu-activated alkaline earth metal phthalate fluorescent system all-metal component element (Ba, The ratio of Sr, Eu, Si) to Si is a composition formula of 3:1 (Bax, Sri x_y, EUy) 2Si〇4 (where 〇&lt;x&lt;tb&lt;y&lt;y.l); all metal The ratio of the constituent elements (Sr, Ba, Eu, Si) to Si is 4:1 composition formula (Sri y, EUy) 3Si〇5 (where 〇&lt;y &lt;0.1), composition formula (3&)1 , 81:1-乂-)^117) 331〇5 (where 〇&lt;\&lt;1'0&lt;7 &lt; 0.1). Further, according to the production method of the present invention, since it is not necessary to synthesize a gel containing an all-metal component uniformly as a pressure vessel of an autoclave, the manufacturing cost is markedly lowered, and thus it is industrially significant. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail, but the embodiments described below are representative of the present invention, and are not limited to the embodiments as long as they do not depart from the gist of the present invention. First, the manufacturing procedure for Eu-activated alkaline earth metal silicate phosphors is described in the paragraph 100118260 11 201202394. The manufacturing process of the present invention is as follows: an aqueous solution (hereinafter, also referred to as an aqueous raw material solution) as a raw material of each element of a pin, a crucible, a pin, or a sand which constitutes a gold subtraction. After mixing the above, the step of maintaining the liquid temperature at 30 to the temperature of the liquid, thereby heating the stone material at a temperature of 30 to ,, and the step of drying the transparent gel in a state in which the total amount of the other metal components is dispersed The step 2 of removing the dried solvent is obtained by drying the transparent gel formed in the step 11; thereafter, the dried product is heat-treated in the atmosphere to obtain a calcined powder, thereby obtaining

Step 3 of activating the soil-based metal lysate phosphor precursor; if necessary, stepping off the coarse particles of 100 /zm or more; by heat treatment of the reducing gas%, forming (5) activating the soil test Step 4 of the metal silicate phosphor. The above steps 1 to 4 will be described in detail. [Step 1] This step is prepared as a raw material water-cooling liquid which is a constituent of a metal component, such as a recording, a crucible, a pin, and a stone stalk. The temperature of C, the step of uniformly dispersing the gel by the total amount of the total metal component of H_. In the first step, the raw material water a liquid of the whole metal component of the pin, the crucible, the pin, and the stone was first prepared. As a raw material for brocade, there is no particular limitation as long as it is dissolved in water and the pH of the aqueous solution is 7 or less. It can be used as a vapor, oxide, 100118260 12 201202394 acetate, nitrate, carbonate, sulfate, oxalic acid. Wind search. In particular, in the case where the anion component can be easily removed by heating, it is preferred to use a nitrate salt, an acetate salt, a carbonate salt, an oxalate salt or the like. Dissolved in the metal salt: Add citric acid, lactic acid, malic acid, etc. In this case, since the composition variation from the addition is suppressed, it is preferable to form a carbonate &lt;aqueous solution having a small solubility as compared with nitrate or the like. The lock raw materials and raw materials are also the same as those recorded. In addition, the raw material aqueous solution of the ship can be separately mixed, and the mixed aqueous solution can be prepared in one container from the beginning. Then, in the present invention, the above-mentioned known water-soluble Shishi compound is used as the raw material of Shixi. When the pH of the solution is more than 7, the water-containing Wei compound immediately starts to gelate and there is a flaw in the formation of a non-uniform gel. Moreover, if the pH is less than 1 ', it is difficult to gel, so the pH is set to! To the scope of 7. Further, when the amount of water relative to the constituent metal element is too large, the gel and the liquid are separated into two layers, and metal ions are eluted in the liquid phase, so that the gel becomes a component of the unevenness. When the amount of water is too small relative to the metal element, it is still impossible to form a uniform aqueous solution, and the metal precipitates before the gel formation to form a gel of an uneven sentence. In the present invention, since the all-metal component element is uniformly dispersed, Or lacking 'It is therefore important that the concentration of the metal S in the preparation of the aqueous solution is set to 1 to 5.5 m〇l/L. Ideally it can be set to 2~5 5 blessings. In the case of the basestone (0.1 mol), 1,2-propanediol (0.4 mol) is added. Here, the specific production conditions of the water-soluble Shishi compound can be produced by the method described in the production example of Cowley Document 3. . #, Relative to the four armor 9 - face use: 100118260 13 201202394 Hot mixer for the ceremony _ — &amp;, mix &amp; 24 hours to make the liquid temperature to 54t, then add hydrochloric acid (0. 〇〇 〇1 Mo/仗/dish is 54C, and after mixing for another hour, it can be obtained as a water-soluble hydrazine solution J in the middle of the production example 1~9 Y in the literature 3. The 匕 有 has a variety of water-soluble people. Any one of the aqueous solutions prepared according to the above conditions can be used in the present invention, and the obtained solution is added to a container at a temperature of 30 1 ° C at room temperature for 1 hour to 1 hour. A uniform gel is obtained. If the temperature is lower than the buckle, the gelation takes time, and the S temperature exceeds i(8). C causes the water to boil, causing both drying and gelation. Therefore, it is important to set the temperature to 30°. More preferably, it is set to 50 to 1003⁄4. The gelation time is not particularly limited as long as it is a uniform gelation time as a whole, and a uniform gel is usually obtained in about 24 hours. Limited, can be made of glass, polypropylene, PTFE, etc. The heat resistance of the heating temperature is [Step 2] Step 2 is a step of removing the solvent from the gel obtained in the step 1 to obtain a dried product. The removal of the solvent is simpler by heating. The solvent component contained is water, ethanol, and propylene glycol, and therefore it is preferably from 1 to 120 ° C. The heating time is also dependent on the amount of the sample, preferably from about 1 to about 6 hours. [Step 3] 100118260 14 201202394 The dried matter in the form of 2 is used to thermally decompose and remove the organic matter in the atmosphere, thereby obtaining the step of the body powder as the body of the ferrite of the alkali metal salt of the salt. The purpose of the money is to return (4) The y-knife solution of the organic matter contained in the situation, the removal of carbon generated by the decomposition, and the growth of the oxide β of the Eu-activated metal citrate phosphor, β, 、, σ. The condition of the heat treatment is based on the temperature of the crucible. The heat treatment can be carried out by heat treatment. Every time heat treatment The milk spider is crushed. The details of the heat treatment are as follows: First, the decomposition of the organic matter causes the propylene glycol contained in the raw material to be graded or thermally decomposed and shouted. In order to burn the organic matter, a temperature of _ or more in the atmosphere is required. When only the decomposition of the organic matter is carried out, it is preferably carried out in an environment of 400 to 600. The carbon removal system completely removes the carbon formed by the decomposition of the above organic matter, and salifies the metal element. In the case of the case, it is decomposed. At a temperature lower than 7 ° C, it is impossible to remove the charcoal, if it exceeds 1300. (: 'There is a case of melting or sintering, so the heat treatment is over 13 (m: temperature) It is carried out in consideration of the heat treatment time. In the case of performing carbon removal alone, it is preferred to carry out 700. (: to 1300. (: The heat treatment in the temperature range 乂 and then in the case of the formation of oxide precursor crystals, is carried out in the atmosphere of calcination. '100118260 15 201202394 Melon burning degree in the oxide mother crystal is Sr3Si〇 In the case of 5, when the degree of collapse is less than 13 〇〇c, it is difficult to obtain a crystalline phase; when it is more than 16 Torr, the reaction is carried out with oxidation! Therefore, preferably & 13(9).c~16 Μt&gt;c μ degree range. Especially preferably 145 〇. (: to 155 〇. If the heat treatment temperature is too low, the SrjiO4 phase which is out of phase is formed as an impurity, and the finally obtained phosphor If the heat treatment temperature is too high, the ShSiO5 crystal is sintered or melted, and it is difficult to obtain a powdery phosphor without pulverization. The pulverized phosphor damages the crystal, so that high-intensity fluorescing is obtained. In the case of the oxide mother crystal (Bax, SivASiOs, (Bax, Sri-x) 2Si04, it is difficult to obtain a crystal phase at a temperature lower than l〇〇〇t: 1600 ° C temperature, with alumina crucible The reaction is carried out, so it is preferably in the range of from 1000 ° C to 1400 ° C. More preferably, it is 12 〇〇. 〇 to 135 〇 ° C. The right heat treatment temperature is too low 'is also a heterogeneous BaC03 phase or SrC 〇 The third phase remains as unreacted impurities, and the luminous intensity of the finally obtained phosphor is lowered. Therefore, if the heat treatment temperature is too high, the calcined product is sintered or melted, and it is necessary to obtain by pulverization. Powdered phosphor. Further, the 'pulverized phosphor damages the crystal, so it is not preferable for obtaining a high-luminance phosphor. The heat treatment time is 1 to 24 hours, preferably 2 to 4 hours. If the heat treatment time is short The reaction to form the parent crystal is insufficient, the purity of the crystal phase is lowered, and the luminescence intensity is low. If the heat treatment time is long, the sintering is improved, and 100118260 16 201202394 is sintered to form hard coarse particles or fixed in the container. Further, the above heat treatment may be performed by heat treatment a plurality of times, or may be subjected to heat treatment once under optimum conditions, and further, may be continuously changed to suit each heat treatment. The heat treatment conditions, the surface is subjected to the heat treatment cycle. Further, when the oxide mother crystal is Si:3Si〇5, if the SrzSiO4 phase which is a heterogeneous phase is formed, it is easy to be sintered at a low temperature compared with the secret phase 5. Therefore, in the subsequent reducing atmosphere of the (4) 4 reducing gas environment, coarse particles are formed to reduce the fluorescence characteristics. Therefore, it is preferable to remove coarse particles of 100 Mm or more in advance by classification. [Step 4]. Step 4 is a step of heat-treating the calcined powder obtained in the step 3 in a reducing gas atmosphere, and replacing the Eu2+ with the divalent europium ion or the divalent europium ion in the parent crystal to obtain a phosphor. The calcined powder used herein may be an oxide which completely decomposes the carbonate in the step 3, or may be a calcined powder in a state containing a part of the carbonate. The temperature (calcination temperature) of the heat treatment differs depending on the composition, the calcination condition, the sintering flux, and the like. When the oxide mother crystal is Sr3Si〇5, it is set to 1300 to 16〇0 in the same manner as in the step 3. 〇, preferably 1450 to 1550 ° C. Further, in the case where the vapor mother crystal is (Bax, sri_x) 3si 〇 5, it is set to 1000 to 1400 ° C, preferably 1000 to 1350 ° C in the same manner as in the step 3. As a reducing gas atmosphere, it is possible to mix 100118260 17 201202394 with 1 to 10 vol% of H2 gas in an inert gas such as N2 or Ar. As described above, by the above-mentioned "step" to "step 4", it is possible to produce a high-brightness Eu-activated alkaline earth metal silicate phosphor having a high purity of the crystal phase of the target and a well-dispersed component element. Furthermore, it can be fully considered and expected that the method for producing the £11-activated alkaline earth metal silicate phosphor of the present invention can also be applied to the production of oxide mother crystals having the composition formula ShSiO4 or alkaline earth metals containing other alkaline earth metal elements in the composition. The case of a citrate-like phosphor. (Embodiment) Hereinafter, the present invention will be specifically described by way of examples. As the Eu-activated alkaline earth metal silicate phosphor, a yellow phosphor of a composition formula (Sq - y, Euy) 3Si 〇 5 (where ' 0&lt; y &lt; 〇. i) was used, and a method for producing the same was shown. The water-soluble cerium compound is referred to Production Example 1 (water-soluble cerium compound A) described in paragraph [0046] of Patent Document 3. The identification and semi-quantification of the crystal phase of the produced phosphor were carried out by X-ray diffraction and Rietveld analysis. The evaluation of the compositional deviation was carried out by quantitative analysis of each element by ICP (Inductively Coupled Plasma) luminescence analysis. The evaluation of the luminescence characteristics was carried out by using a fluorescence spectrophotometer FP-6500 (manufactured by Sakamoto Optical Co., Ltd.), and the excitation and luminescence spectra were measured. Further, in the case of 100118260 18 201202394, the luminescence spectrum was measured by setting the excitation light wavelength to 455 nm, and the excitation spectrum was measured at the peak wavelength of the luminescence spectrum. (Example 1) An Eu-active vitate camping body of the composition formula (Sri_y, Eu y) 3Si〇5 (wherein '0&lt;y&lt;〇.l) was produced by the following procedure. [Step 1] As a metal ruthenium compound, SrC〇3 (3N, manufactured by Kanto Chemical Co., Ltd.), Eu(N03)3 · 6h2〇 (3N, manufactured by Sanjin and Chemicals Co., Ltd.) was weighed to make (Sr y, EUy) 3Si〇5 is y=〇〇b in the aqueous solution of citric acid (98.0%, manufactured by Wako Pure Chemical Industries Co., Ltd.), and the total concentration of erroneous and yttrium is added (hereinafter, referred to as metal). The concentration of the salt (Sr+Eu) aqueous solution was 4.0 m, and the amount of 〇3 was weighed, and the clear solution was obtained by stirring off for a few hours. Further, the weighed Eu(10)3)3.6H2〇 was dissolved in water to obtain an aqueous solution. Then, the ^ σ system is added with 1,2-propanediol (〇4苴, 、4 耳) relative to the tetradecyloxylate (〇), while using a heating stirrer to make the liquid The temperature has become 5 generations. Thereafter, the addition of hydrochloric acid (10)^ is 5 generations, and is combined with the Shuiqing compound, and the "SrCOw solution is combined, and the solution is mixed with the sputum. The bonding is carried out for 3G minutes" and the obtained 100118260 201202394 gel has elasticity, [Step 2 Without separating into 2 layers 'According to the appearance of a uniform bear (10) The transparent gel obtained in the step 1 was kept in a dry machine for 6 hours, and the solvent in the gel was removed to obtain a dried gel. Condensed ^ Transparent S1 body shape. Leaf peak is [Step 3] The dry (4) obtained in the step 2 towel is crushed in the Mawang material, and it is carried out in an electric furnace in the atmosphere of the brothers at '55 〇. 〇 3 hours After heat treatment, take out and crush, again in _. 〇: carry out 3 hours of reduction. After escaping and crushing, hold at 1200C for 3 hours, continue to heat up to 15 〇 (rc, keep for 3 hours, in the atmosphere) The heat treatment is carried out, taken out and crushed, and the coarse particles having a size of /zm or more are removed by classification to obtain a calcined powder. [Step 4] The calcined powder obtained in the step 3 is charged into a reversing container, and the crane is heated. In the electric furnace, 'at 1500 C' is connected to a4% H2 + 96% Ai^ in 3 hours. The powdered phosphor powder was obtained by heat treatment of the surface T. The results of the χ 贱 riding of the obtained phosphor powder are shown in Fig. 1. The results of the measurement of the fluorescence characteristics are shown in Fig. 2. In the X-ray diffraction results of Fig. 1, it is known that the obtained phosphor powder is a substantially single phase of ShSiO5. Further, in the fluorescence characteristics of Fig. 2, a broad excitation is found across 3〇〇~5〇Onm. Absorption, the peak is displayed near 585, and it is confirmed that the yellow light is displayed for comparison. YAG: Ce, 100118260 201202394 The luminescence spectrum is more vivid, and the peak intensity of the luminescence and the peak area of the luminescence are larger, and the composition of high luminance is obtained. (Sivy, Euy) 3Si〇5 (wherein, 0 &lt; y &lt; 0.1) Eu-activated citrate phosphor. (Example 2) In addition to Example 1, the total aqueous solution concentration of lanthanum and cerium was set. A phosphor powder was produced in the same manner as in Example 1 except that it was 2.0 mol/L. The results are shown in Table 1. (Example 3) In addition to Example 1, the concentration of the aqueous solution of the total of lanthanum and cerium was set. A phosphor powder was produced in the same manner as in Example 1 except that it was 5.5 mol/L. The results are shown in Table 1. (Comparative Example 1) A phosphor powder was produced in the same manner as in Example 1 except that in Example 1, the aqueous solution concentration of yttrium and lanthanum was 0.1 mol/L. The results are shown in Table 1. (Comparative Example 2) A phosphor powder was produced in the same manner as in Example 1 except that in Example 1, the aqueous solution concentration of yttrium and lanthanum was 0.15 mol/L. The results are shown in Table 1. (Comparative Example 3) A phosphor powder was produced in the same manner as in Example 1 except that in Example 1, the aqueous solution concentration of yttrium and lanthanum was changed to 0.2 mol/L. 100118260 21 201202394 The results are shown in Table 1. (Comparative Example 4) In the first embodiment, the phosphor solution powder was prepared in the same manner as in the case of the actual age, by setting the aqueous solution concentration of the total of the recording and the pin to 6.0 mol/L. The results are shown in Table 1. [Table 1] Comparative Example 1 Metal salt (Sr+Eu) water-[mol/L] The ratio of the moisture content of the two-layer separation from the gel separation [wt%] There are 20.2 WS weights 1 1 Z Z Comparative Example 3 Example 2 Example 1 Example 3 Comparative Example 4 ----0.15 There are 2.6 ——-^0.20 Yes (although only a little) 0.8 —^_2.〇〇No 0.0 — — No 0.0 No 0.0 ----6.00 I. - According to Table 1, it is known that the metal salt (Sr+Eu) 7jc solution has a low concentration, the knife is separated from the layer and the moisture content from the gel is increased. 'If the concentration of the metal salt (Sr + Ειι) Α 4 is increased 'The financial separation is two layers, * a transparent gel with a uniform sentence state. Further, if the concentration of the aqueous solution of the metal salt (Sr+Eu) was 6 m〇1/L (Comparative Example 4), the metal salt could not be completely dissolved. Therefore, in order to uniformly disperse the metal component halogen (Sr + Eu) in the gel, the concentration of the metal salt (Sr+Eu) aqueous solution can be set to 1 to 5.5 m〇i/L, and preferably 2 can be set. ~5 5 mol/L. (Example 4) A phosphor powder was produced in the same manner as in Example 1 except that the holding temperature at the time of gelation in the step i of Example 1 was changed to 80 Å: = 'mesh 100118260 22 201202394 The results of the gelation state of the sample are shown in Table 2. In addition, the criteria for judging the gelation described in Table 2 are set to "〇" when the container is shaken or reversed, and the case where the fluidity of the city is "X". (Example 5) A spunlace powder was produced in the same manner as in the case of the actual off 1 (4) except that the temperature at the (4) temperature of the step 1+ of Example 1 was set to be aeronautical. The results of visual observation of the gelation state of the sample are shown in Table 2. (Comparative Example 5) A phosphor powder was produced in the same manner as in Example except that the holding temperature at the time of gelation in the step i of Example i was 25 °C. The results of visual observation of the gelation state of the sample are shown in Table 2. (Comparative Example 6) The holding temperature was changed to 25 except for the gelation in the step 1 of Example 1. (: The phosphor powder was produced in the same manner as in Example ^ except that the holding time was set to 96 hours. The results of visual observation of the state of the sample were shown in Table 2. [° Table 2]

According to Table 2, at the time of gelation, even if it was kept at 100118260 23 201202394 24], the gel still had fluidity, and even after 96 hours, the gripping property remained, and it could not be in a uniform state. On the other hand, in the range of 50 〇C to 100 C, either of them may be separated into two layers to obtain a transparent gel in a uniform state. (Comparative Example 7) In the second step of the first embodiment, the transparent mixed solution was placed in a polytetrafluoroethylene and a valley, and placed in a pressure-resistant container made of stainless steel, sealed, and kept at 2 ° C for 24 hours. The sample obtained by gelation contains a gel and a liquid, and is separated into two layers. The weight of the liquid separated from the gel was 2% mass % of the whole. The gel-dried powder obtained in Example 1 of the money -7 was subjected to a component (Sr, Eu,

The results of the analysis, comparison and addition of the composition of Sl) are shown in Table 3. [Table 3] Element ratio ^i§ii_Si+Eu) ^i§I±_Si + Eu) i^r+Si + Eu)

★Additional composition Example 1 I Example -0.31 0.25 0.06 Comparative Example 7 -4.07 3.92 0.15 According to Table 3, the ratio of the amount of Sr contained in the gel of Comparative Example 7 relative to the total amount of .S! Less, the deviation from the added composition is larger, and the ratio of the amount is larger. As shown above, the temperature at which the gelation is maintained is important in the present invention, and is an important factor for the formation of a uniform composition. [Comparison of quantum efficiency] 100118260 24 201202394 The measurement is performed using an integrating sphere and found in Example 1. The results of the quantum efficiency in the workability of the obtained phosphor particles (measured by the wavelength of the excitation light: Ex = 455 nm) are shown in Table 4. For comparison, as a prior example, general YAG: Ce was measured as a general yellow phosphor. [Table 4] Absorption rate [%] External quantum efficiency [%] Internal quantum efficiency [%] Example 1 79.3 56.3 71.1 Previous example: YAG: Ce 73.0 47.8 65.5 According to Table 4, in Example 1, internal quantum efficiency It shows a very high value of 71.1%, which is superior to the previous YAG: Ce phosphor. (Example 6) Subsequently, Eu-activated alkaline earth metal citrate fluorite of the composition formula (Bax, Sri-xy, Euy) 3Si05 (where 0 &lt; x &lt; 1, 0 &lt; y &lt; 0.1) was produced by the following procedure conditions Light body. In the same manner as in Example 1, except that in the first embodiment, the cerium carbonate was weighed, a phosphor powder was prepared in the same manner as in Example 1 except that strontium carbonate and cesium carbonate were set to have a molar ratio of Sr: Ba of 0.86 : 0.13. That is, the soil-based metal silicate phosphor is activated for Eu represented by the composition formula (BaG.86, Sr0.13, Eu0.G1)3SiO5. When the obtained phosphor powder was subjected to X-ray diffraction measurement, it was found that no carbonate or other impurity phase was observed, and the phosphor powder was substantially single phase. Further, the fluorescence characteristics were measured. As a result, as shown in Fig. 2, it was found that there was a peak excitation excitation near 350 nm, and the luminescence system showed a peak at around 600 nm, which was confirmed to be orange luminescence. 100118260 25 201202394 Therefore, a Eu-activated alkaline earth metal silicate phosphor having a high luminance composition formula (Bax, Sr]-x-y, Euy) 3Si05 can be obtained. (Example 7) An Eu-activated alkaline earth metal silicate phosphor having a composition formula (Bax, Sq-x-y, Euy) 2Si04 was produced by the following procedure. [Step 1] As a metal element compound, weighed BaC03 (3N, manufactured by Kanto Chemical Co., Ltd.), SrC03 (3N 'made by Kanto Chemical Co., Ltd.), and Eu2〇3 (3N,

Furuchi Chemical Co., Ltd.), in the formula (Bax, Srh_y, EUy) 2Si〇4 becomes x = 0.69 y = 0.08. It is added to an aqueous solution of citric acid (98.0%, manufactured by Wako Pure Chemical Industries Co., Ltd.) so that the total amount of lanthanum, cerium, and lanthanum (hereinafter referred to as the concentration of the aqueous solution of the metal salt (Sr + Eu) becomes * m〇1 The BaC03 and SrC〇3 weighed in /L, at 4 〇th, thereby obtaining a transparent solution. In addition, weighed Eu (3·6Η2〇 dissolved in water to obtain aqueous solution 0 and then wr玍矽 compound relative to tetradecyloxydecane (7)), and added 1,2-propanediol (〇.4mol) - Mixing the surface for 24 hours to make the liquid temperature 5 generations. The second heat is used to make the main solution, and then add hydrochloric acid (〇.〇 (mole) to make 14 54C, and the cutting compound

The solution and the SrC03 solution were touched by a person and mixed with BaC 3 overnight, and mixed at room temperature to obtain a transparent mixed solution. Kawasaki clock

The mixed solution prepared as described above was placed in a polypropylene-made 100118260 1 M 26 201202394 lid to be sealed, and a clear gel was obtained at 5 (rc retaining gel, not separated into 2 layers, ', hour'. Step 2] ^ According to the appearance of uniformity. The permeation obtained in step 1 is 6. ^ in a dryer, and at 12 (TC is kept at M, the solvent in the gel is removed 〒 is transparent _&amp;彳 彳 燥 。 dry dry gel [Step 3] The dryness obtained in step 2 is then crushed from the broken gel in the mash, using an electric furnace in the atmosphere, at 550. :Into the rod ^, Shi T3 hour heat treatment, take out and press = after 're: people in the series for 3 hours of heat treatment. After taking out and crushing, ^ in the mGG_ 6 where the field of reduction and crushing, and Obtain the pre-calcined powder. [Step 4]: In the pre-burned powdered man-made molybdenum container obtained in step 3, use the electric heating furnace, at 12003⁄4, with 3 hours眛, “, L “3 hours 1 pass A 2 + 96% Ar mixed gas is heat-treated to obtain a powdery phosphor powder. The obtained phosphor powder is subjected to χ-ray winding. As a result of the experiment, it was found that no carbonate or other impurity phase was found, and the results of measuring the fluorescence characteristics of the work powder powder α α are shown in Fig. 3. '', early phase. In the fluorescence characteristics of Fig. 3, It was found that there was a peak excitation excitation near 37 〇 nm, and the luminescence system showed a peak near 529 nm, which was confirmed to be a green luminescence to obtain a high-luminance composition (Bax, Sri_y is) Qian Zhiru ^ soil test. W0118260 27 201202394 Acid Silide (Comparative Example 8) The heat treatment temperature in the atmosphere of Step 3 was set to 13 〇〇. 〇, the heat treatment temperature in the reducing gas atmosphere of Step 4 was set to be 13 〇〇〇c' An Eu-activated alkaline earth metal silicate phosphor of the composition formula (Bax, Sr^-xy, Euy) 2Si〇4 was synthesized in the same manner as in Example 7. After step 4, 'sintering the sample hardened' was obtained. The powdery sample was pulverized. The fluorescence characteristics of the sample after the pulverization were evaluated. As a result, as shown in Fig. 3, it was found that the excitation absorption at the peak of 370 nm was observed in the same manner as in Example 7, and the luminescence was obtained at 529. Peak is displayed near nm, but compared to Example 7 The sample showed poor luminescence intensity. (Comparative Example 9) The heat treatment temperature in the reducing gas atmosphere of the step 4 was set to iooo^ except that the heat treatment temperature in the atmospheric environment of the step 3 was set to 10 〇 0 〇 C. The Eu-activated alkaline earth metal silicate phosphor of the composition formula (Bax, Sq-xy, Euy) 2Si〇4 was synthesized in the same manner as in Example 7. The fluorescence characteristics of the sample were evaluated, and the results are shown in Fig. 3. In the same manner as in Example 7, it was found that there was a peak excitation excitation near 370 nm, and the luminescence showed a peak near 529 nm, but the sample 'light emission intensity was much worse than that of Example 7> as described above using the examples and As described in the comparative example, according to the manufacturing method of the composition of the present invention (Sq-y, Euy) 3Si05 (wherein 〇 &lt;y&lt;〇.i), Eu-activated phthalate fluorescent 100118260 28 201202394 can be obtained. A localized yellow phosphor having a broad range of excitation absorption from ultraviolet to blue and having a light-emitting band around 585 nm. Further, according to the composition formula of the present invention (Bax, Sr xy, Euy) 3Si05 (where ' 0&lt; χ &lt; 1, 〇 &lt; y &lt; y. l) Eu-activated soil-like metal fluorite fluorescence In the method for producing a body, a high-intensity orange phosphor having a wide range of excitation absorption from ultraviolet light to blue and having a light-emitting band around 600 nm can be obtained. -y, Euy) 2Si04 (where 0, in addition, the composition formula according to the present invention (Bax, Sh-

a X &lt;χ&lt;1 〇&lt;乂&lt;〇.1) Eu-enhanced soil-like metal-metal lithite glory

[Simple description of the map]

For comparison, the commercially available YAG: Graphs of the fluorescence spectra of Examples 8 and 9 are also displayed together with • Ce (spectrum of the previous example). 100118260 29

Claims (1)

201202394 VII. Patent application scope: 1. A method for producing Eu-activated alkaline earth metal silicate phosphor, which is composed of Sri-y, Euy 3Si05 (where 〇&lt;y&lt;〇.i) , composition (Β &amp; χ, Sr) - xy, Euy) 3Si 〇 5 (where 〇 &lt; x &lt;; 1, 〇 &lt; y &lt; 〇 1), composition formula (Β &amp; Sq-xy, Euy) 2Si A method for producing an Eu-alkaline earth metal silicate phosphor selected from the group consisting of 〇4 (wherein 〇&lt;χ&lt; 丄, 〇&lt;y&lt;〇&gt;) is characterized by 'including the following step 1: [Step 1] An aqueous solution of each of the raw materials of the respective constituents of cerium, lanthanum, cerium, and lanthanum constituting the metal component is prepared, and the mixed aqueous solution of the aqueous solution prepared by mixing is maintained at a liquid temperature of 30 to 100 c, thereby forming an all-metal The step of gelling the state in which the total amount of the components is uniformly dispersed. 2. A method for producing Eu-activated alkaline earth metal silicate phosphor, which is a self-composition formula (Sri-y, Euy) 3Si05 (where 〇&lt;y&lt;〇.i), composition formula (Sr! -y,Euy)3Si05 (where 'ocycoj) (Bax,Srbu EUy)3Si〇 is where 'o&lt;x&lt;n'o&lt;y&lt;0·', composition formula (Bax,Sri_x_y,EUy)2Si〇4^ A method for producing a rib-derived alkaline earth metal silicate phosphor selected from the group consisting of 〇&lt;X<卜〇&lt;y&lt;〇.l), comprising the following steps 1 to 4: [Step 1] The aqueous solution of each of the raw materials of the respective constituents of ruthenium, osmium, iridium, and osmium, which constitute the metal component, is prepared, and the mixed aqueous solution of the aqueous solution prepared by mixing is maintained at a liquid temperature of 30 to 1 Torr, thereby forming a step of uniformly dispersing a gel of a state of 100118260 30 201202394 in a total amount of all metal components; - [Step 2] a step of drying the gel formed by the step 1 to form a dried product, and removing the solvent contained therein [Step 3] The above dried product in the step 2 is heat-treated in an atmosphere to remove the organic matter. And the step of obtaining the calcined powder; [Step 4], the step of obtaining the phosphor powder by the heat treatment of the above-mentioned Lai powder reduced by the step 3 in the refining gas environment. 3. If the patent application scope is 1 or (2) A method for producing a soil-grown metal-metal oxide body light body, wherein the concentration of the constituent metal in the mixed aqueous solution in the above step i is set to 5.5 mol/L 4. For the manufacturing method of Eu-activated alkaline earth metal strontium® salt phosphor of the second item of the patent application, or the second item, the water 3 liquid of the raw material in the step 1 is attached to the fourth layer. Adding oxetane and 2-propanol to oxydecane and heating, stirring, and mixing; then adding hydrochloric acid to form a water-soluble hydrazine aqueous solution. 5. Applying the ferrite of the light body of the second item of the patent scope The metalloprolate-like method, wherein the method comprises the step of removing the coffee (4) from the calcined powder formed in the above step 3 by the above-mentioned step 3, and removing the coarse particles.