TW201011092A - Aluminate phosphor and preparation method thereof, and fluorescent lamp and liquid crystal display device using the aluminate phosphor - Google Patents

Abstract

The present invention relates to an aluminate phosphor represented by the general formula (Ce.sub.xTb.sub.1-x).sub.2O.sub.3.y(Mg.sub.1-zMn.sub.z)O.nAl.sub.2O.sub.3 (provided that when 0 < x < 1, x, y, z, and n satisfies the conditions of 0.6 ≤ y ≤ 1.8, 0 ≤ z ≤ 1, 7 ≤ n respectively, when x=1, x, y, z, and n satisfies the conditions of 0.2 ≤ y ≤ 1.8, 0.1 ≤ z ≤ 1, 7 ≤ n respectively). Compared to the conventional phosphor, it can significantly increase brightness, also, significantly reduce 1 / 10 decay time. Also, the use amount of the rare element Tb can be reduced. The aluminate phosphor can suitably be used in a fluorescent lamp for lightening, or a backlight lamp, particularly by using an aluminate phosphor with short 1 / 10 decay time as a backlight lamp, and making it light intermittently to provide a liquid crystal display device with excellent animation features.

Description

201011092 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a green light-emitting aluminum acid exhibiting higher brightness than before, under excitation by ultraviolet light and vacuum ultraviolet rays (especially 18 〇 nm to 3 〇〇 nm). Salt phosphor. In particular, in the case of Μη as a green luminescent precursor, the luminescence intensity of about 2 times that of the previous phosphor is exhibited, and, by its structure, it is alive with the current circulation of Eu.Mn. A cerium-activated aluminate phosphor having a more excellent lifetime of a bulk (hereinafter referred to as βαμ phosphor) (BAM: Eu, Mn), and a method for producing the phosphor. Further, the present invention relates to a fluorescent lamp excellent in brightness and color reproduction range using such an I lynate phosphor, and particularly preferably a cold cathode fluorescent lamp. In addition, 钸·Magnesium·aluminate phosphors and ΤΙ··Μ 共同 呈现 © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © The present invention relates to an ultraviolet light and a vacuum ultraviolet ray, particularly an ultraviolet ray of 180 nm to 30 〇 nm, which has approximately the same brightness as the prior material, and the residual light time is greatly shortened, and the material cost can be reduced. Green-emitting Tb-activated bismuth-magnesium-aluminate phosphor. Further, the present invention relates to a fluorescent lamp having a short afterglow time using such a phosphor, and particularly preferably a cold cathode fluorescent lamp. The present invention relates to a display using such a phosphor, and particularly preferably a display using a backlight element of a cold cathode fluorescent lamp using the phosphor of 098124986 201011092. [Prior Art] Conventionally, as an aluminate-based green light-emitting phosphor, a Tb-activated yttrium-magnesium aluminate phosphor (hereinafter referred to as a CAT phosphor) and Eu·Μn are known. Revitalizing 钡•Magnesium·aluminate phosphors, etc. However, in recent years, the price of Tb has risen remarkably, and it has been difficult to escape the decrease in color purity caused by the light emission of Tb^light, which has a problem of short life in BAMf light bodies. In such a case, as a neo-coloring body which exhibits high-intensity green light emission by ultraviolet light excitation, for example, a 钸······························ Reference is made to the patent document and the &amp;acid phosphor in which the part of Mg of the phosphor is substituted with another valence metal element (for example, refer to Patent Document 2 to sentence, etc. However, the market towel is often expected Developed a phosphor that emits light with higher brightness than the previous product, for example, regarding the use of ultraviolet light generated by a cold cathode fluorescent lamp (a rare gas such as Ar or Xe other than mining, and which is generated by discharge) Green, luminescent phosphors for fluorescent films with vacuum ultraviolet and line-excited filaments are also expected to develop phosphors that produce brighter and brighter green luminescence than previous substances. Μ 赋 赋 钸 钸. Magnesium. Ming acid is a glory body, in the case of the shoulder is not alive _, in the near ultraviolet region from Ce (350ηη, near Can be excited and presented In the green wavelength region of the divalent (4) coffee 098124986 201011092 (near), there is a peak of luminescence. Therefore, this Μ 赋 赋 镁 镁 镁 magnesium aluminate phosphor is 'in order to be excited by ultraviolet rays (especially 18 〇 nm to 300 nm) On high-brightness green luminescence, the energy absorbed by trivalent Ce must be efficiently reabsorbed by Μη (ie, energy transfer). Therefore, the luminescence from the outer region of Ce is not transmitted by Ce. The luminescence to the Μη portion is invisible to the naked eye, and since it does not contribute to the illuminating intensity, it is also desirable to suppress it as much as possible and to increase the intensity of the luminescent light in the green light region. Also, as the aluminate-like green of its structure One of the luminescent phosphors, a bismuth magnesium aluminate phosphor (hereinafter, also referred to as a CAT phosphor) which is activated by the above-mentioned Tb, and a bismuth magnesium aluminate which is co-activated by Tb · Μ Phosphor (hereinafter, also referred to as CAT: Μη phosphor). These well-known CAT phosphors ((ce, Tb) MgAln019" and CAT: Μ 萤 phosphor "(Ce, Tb) (Mg, Mn The stoichiometric composition of Alu〇i9, which is often (Ce+Tb): Mg (Ce + Tb): (Mg + Mn) is about 1: 1 (i.e., the phosphor composition molar ratio of Ce + Tb and each of Mg, or

The composition of Ce+Tb•. is approximately equal to the molar ratio of Mg+Mn. - For example, in Patent Document 5, the proposal is composed of

(Mgl.aMna)〇. χΑ!2〇3 . yCe2〇3ZTb2〇3 ^ CAT · Μη J In this composition formula, (Ce.Tb) : (Mg + Mn) is still fixed at 1: The increase in the amount of substitution causes the brightness to change. Further, in the straight n i' liter document 6, a part of the composition is disclosed as 098124986 5 201011092 (l/2-x-y) Ce2〇3 · xLa2〇3 · yTb203 · MgO · ρΑ1203

In a CAT phosphor in which Ce is substituted with La, even if the p-value (amount of Al2〇3) is increased by the stoichiometric composition, a light beam which is comparable or slightly higher than the stoichiometric composition can be obtained. In addition to the green luminescent phosphors that are activated with respect to this Tb or Tb and Μη, it is also desirable to develop a phosphor that emits green light of higher brightness than the prior material. Further, recently, in response to the demand for a green phosphor, in addition to the improvement in brightness, short-lived photochemical is exemplified. That is, a liquid crystal display (LCD) is formed by combining a backlight and a crystal shutter to form an image on a flat plate, and a color filter can be combined to display an image in color. In the LCD, all the pixels are displayed at the same time, and the fixed display is often displayed until the image of one frame is replaced by the next frame. In this fixed display, because of the characteristics of the residual image felt by the human eye, the afterimage feeling is not lost in the intense image such as the sports Langmu, and is only a very image with a residual image. Incidentally, the number of display segments of the 'TV image signal in the world' is about 5G to 6G frames in one second. In Japan, it is also 6 frames per second. The display time of a frame is about 16msec. With the advancement of technology, the response of the liquid: is shorter than 16_e and the afterimage feeling is lower (four) but only increases the speed of the application, and its higher effect is weak, for example, even if the response speed is 098124986 201011092 0msec Make the afterimage disappear. Thus, in the case of the LCD towel, (4) the simple (four) handle towel must have the same degree of animation characteristics as the pulsed display color brown tube (CRT). In order to make the residual image in (10), for example, in the past, the display of 60 frames per second was raised by U_120 frames, the fixed image was shortened to half of the brain C, and each of the wheel powers was used. The image signal of the frame part is displayed in black on the full face, so that the illumination timing of the backlight is selectively performed, or the combination of both is realized, and the animation characteristic close to crt is obtained under the pseudo-pulse display. On the other hand, in order to reduce the residual image of the LCD and the blur of the rim, it is attempted to cause the cold cathode glory lamp (CCFL) used for the backlight to be displayed in full-frame black at the same time and flashed. Even with the 6 GHz frame cycle number, it can be accelerated to more than ΠΟΗζ in recent years, which can shorten the CCFL lighting time and turn off time. Therefore, regarding the phosphor used in the above CCFL, it is desired to develop a phosphor which may have a short afterglow time. In the past, as a liquid crystal backlight (4) CCTL, an m-shaped fluorescent lamp has been used. In such a three-wavelength fluorescent lamp, a light-emitting spectral peak having a strong and half-value width narrow is used in the vicinity of wavelength regions of 450, 540, and 610 nm. Blue, green, red phosphor. The representative 1st CCFL uses a red phosphor with a 1/10 afterglow time of the active cerium oxide phosphor (hereinafter also referred to as YOX phosphor), which is about 3 〇ms, and the representative CCFL uses blue fluorescing. The 1/10 afterglow time of the photoreceptive active aluminum strontium aluminate phosphor (hereinafter, 098124986 7 201011092 also known as BAM glory) is less than l.Gms, and relatively 'usually used as a representative for CCFL now. The 1/10 afterglow time of the Ce and Tb #-activated phosphoric acid phosphors (hereinafter also referred to as LAp glare) of the green phosphor is 7.4 ms. Among these red, blue, and green phosphors, the residual light time of the green phosphor is longer than the other two colors, and the green light of the 54 Gnm wavelength region has a problem of significant green residual light because of the higher visual sensitivity. . On the other hand, as the green phosphor other than the above-mentioned LAP phosphor, the Tb· Μ η 共同 · · · · · ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( And magnesium-aluminate phosphor (hereinafter also referred to as CAT phosphor) which is activated by Tb. However, the CAT: Μη phosphor described in Patent Document 7 has a long residual light emission with the above-mentioned LAP phosphor, and is disadvantageous for use as an LCD backlight requiring short afterglow. Regarding the CAT phosphor, for example, according to Non-Patent Document 1, from the viewpoint of brightness, 'Ce : Tb = 2 : 1 (ie, Ce / Tb = 2.0), Mg : (Ce + Tb) = 1 : 1 (ie, Mg/(Ce+Tb)=l.〇) is most appropriate, but such ratios do not make the 1/10 afterglow time satisfactory. In addition, in the present specification, the 1/1 〇 afterglow time means a time required for the phosphor to be irradiated with ultraviolet rays to illuminate the luminescence intensity immediately after the excitation light is blocked to 1/10 brightness. Prior Art Document 098124986 8 201011092 Patent Literature

Patent Document 1: Patent Document 2: Patent Document 3: Patent Document 4: Patent Document 5 = Patent Document 6 = Patent Document 7 = 曰 Patent Patent Publication No. Sho 49-77893, Japanese Patent No. 2663306 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

Non-Patent Document 1: j. Electrochem. Soc., SOLID-STATE SCIENCE AND TECHNOLOGY (Dec. 1974 P1623-1627) A Survey of a Group of Phosphors, Based on Hexagonal Aluminate and Gallate Host Lattice (JMPJ Verstegen) [Summary of the Invention] ❹ (Problems to be Solved by the Invention) The present invention provides green luminescence which exhibits higher brightness than prior substances under vacuum ultraviolet and ultraviolet excitation, and illuminates the visible light region of the prior product compared to the near ultraviolet region. An aluminate phosphor which is high in strength and excellent in absorption of mercury rays, an aluminate phosphor which is activated, a method for producing the phosphor, and a general illumination lamp and a cold cathode fluorescent lamp using the phosphor are the subject. Further, the other subject of the present invention is to provide a high-brightness green luminescence which exhibits the same or higher than that of the prior substance under vacuum ultraviolet ray and ultraviolet ray. 098124986 9 201011092 Living decoration magnesium aluminate phosphor and Tb ΜηCommonly revitalized. Magnesium·aluminate phosphor. Furthermore, the subject of the present invention is that under ultraviolet light and vacuum ultraviolet rays, particularly ultraviolet light of 180 nm to 300 nm, the light-emitting time is approximately equal to that of the prior material, and the residual light time is greatly shortened, and the material can be reduced. A magnesium-aluminate phosphor, a method for producing the phosphor, and a cold-cathode fluorescent lamp using the phosphor, which is a green light-emitting Tb-activated product, is a problem. (Means for Solving the Problems) In order to solve the above problems, the inventors of the present invention have repeatedly examined the relationship between the prior activity of the active magnesium oxide and the phosphoric acid (four) and the light-emitting characteristics such as brightness. As a result, by synthesizing the stoichiometric composition of the prior homologous aluminate phosphor (hereinafter, the previously known Μη is activated 钸·錤· = acid, the ce..Mg+Mn of the phosphor is about 1: i The composition is abbreviated as "stoichiometric composition". The composition of the deviation is such that the absorption of the excitation light is nearly doubled, and the energy transfer efficiency from Ce to Μ is also improved (from Ce to 35 〇 nm). The ratio of the nearby luminescence to the luminescence intensity from the vicinity of Mni 517 nm changes to the direction in which the luminescence from Μη becomes larger, and the luminance of the green luminescence is found to be remarkably improved, and the present invention has been attained. Thus, the Μη-activated aluminate-based phosphor of the present invention (hereinafter, simply referred to as "aluminate phosphor" of the present invention) constitutes a content ratio of each metal element of the phosphor, and is stoichiometrically The composition is staggered, and thus the stoichiometric composition of 098124986 10 201011092 staggered (indefinite ratio) causes a change in the crystal structure of the phosphor and a change in the Y quality (light-emitting property), and it is presumed that the properties are excellent, ^ b The phosphor of the method' has been found by the inventors to be limited to the fact that the yin is only limited to the same degree as the phosphor activated by Tb or Tb only. As a result of the review, ❿ (the decrease of Ce in the phosphor of 0° with respect to the amount of Tb (mole) is

Ce/Tb&gt; 2.0 (Morbi), («Ce + Tb in the phosphor is less than the amount of Mg (Mole), ie, 'Mg/(Ce + Tb)&lt;l.〇( Mohr's, (γ) combination of such a decrease in the amount of Tb and a decrease in the amount of Mg, a green phosphor having approximately the same brightness as the previous substance and having a significantly reduced afterglow time can be obtained. The present inventors have also found that if the green phosphor is used in a white fluorescent lamp, the decrease in brightness can be further suppressed. It is considered that since the amount of Tb in the phosphor is reduced, the Ce emission is increased. Further, since the light emission of Tb is lowered, the brightness tends to decrease. However, since the Ce light emits light to excite other color phosphors (red phosphor, blue light body), the white light does not reduce the brightness as such. In the LCD, due to the residual image and the blur of the contour, the backlight is flickered, and the step of further shortening the interval of the backlight flashing is adopted. The 098124986 ^ 201011092 type of salt reading is characterized by the general formula: (1) 'This flashing mode must start brightly in an instant, so the decay time (after-light time) is short. The start time is also short, so it is advantageous for the brightness. The present invention has been completed based on the following findings, and the following are the main points: ° (CexTbl x) 2 ° 3 · y (MSi-zMnz) 〇 - π Α 12 〇 3 ( However, in the formula, 'x, y, z, and η are respectively 〇&lt;χ&lt;ι, which are the numbers satisfying the conditions of (4) d8, 〇$zy, and 7$n, χ==ι, to satisfy ~called ^ 8 (2) The number of conditions of 7Sn is shown in (2) as described in (1) above, in the above general formula, 'x = 〇. 3Sy each 1.2 〇 (3) as described in (2) above And the aluminate phosphor according to any one of the above (2) or (3), wherein the aluminate phosphor according to any one of the above (2) or (3), Wherein, in the above general formula, η in the formula is 12$η$40. (5) an aluminate phosphor which is at least composed of cerium (Ce), manganese (Mn), magnesium cerium (Mg), A phosphor composed of aluminum (Α1) and oxygen (〇) is characterized in that the ratio of the emission intensity at 350 nm to the emission intensity at 518 nm is less than 15% when excited by ultraviolet light having a wavelength of 254 nm. (5) The aluminate phosphor described in the above, wherein the phosphor is one (CexTbk);^ · yiMguJVlnOO · ηΑ1203 means, and in the general formula, x, y, z, and η are respectively satisfied χ = 1, 〇.2$y$1.8, 0·1$Ζ$1, 7$ The aluminate phosphor according to the above (1), wherein X is 0 &lt; x &lt; l, y is 0.8 SyS 1.6. (8) The aluminate phosphor according to (7) above, wherein, in the above general formula, X is 0.5 S xS 0.9. (9) The aluminate phosphor according to any one of the above (1) to (3) wherein, in the above general formula, η is ll^n. (10) The aluminate phosphor according to any one of the above (7) to (9) wherein, in φ, in the above general formula, z is z=0. (11) The aluminate phosphor according to (1) above, wherein in the above general formula, 0.68 S x S 0.95, z = 0. (12) The aluminate phosphor according to (11) above, wherein, in the above general formula, 〇.7Sx$0.85. (13) An aluminate phosphor which is a phosphor composed of at least cerium (Ce), cerium (Tb), magnesium (Mg), aluminum (A1), and oxygen (0), which is characterized by 1 The /10 afterglow time is below 6.4ms. (14) The aluminate phosphor according to any one of the above (1) to (13) wherein the surface is coated with a coating material. (15) The aluminate phosphor according to the above (14), wherein the coating material is a carbonate of a rare earth metal. (16) The aluminate phosphor according to the above (15), wherein the rare earth metal carbonate is coated in an amount of 0.05 to 5% by weight based on the amount of the phosphor. (17) A method for producing an aluminate phosphor characterized by Ce, Tb, 098124986 13 201011092

The stoichiometric composition formula of Mg, Μη, and A1 is a ce compound, a Tb compound, a Mg compound, a Μ 化合物 compound, and a ratio according to any one of the above (1) to (4), and (6) to (12). The A1 compound is mixed and calcined. (18) A method for producing an aluminate phosphor characterized by having a stoichiometric composition formula of ce, Tb, Mg, Μ, and A1 by the above (1) to (4), and (6) to (12) The ratio described in any one of them is: a Ce compound which can be converted into an oxide of cerium (Ce), a Tb compound which can be converted into an oxide of cerium (Tb) by heating, and can be changed into magnesium by heating (Mg) The Mg compound of the oxide, the Mm chelate compound which can be turned into an oxide of 猛η, and the A1 compound which can be turned into an oxide of the slag (A1) are mixed and calcined. (4) The aluminate phosphor described in any one of the above (1) to (10). (20) The fluorescent lamp according to (19) above, wherein the fluorescent lamp of the middle 〃T ′ is a cold cathode fluorescent lamp. (9) A cold-cathode fluorescent lamp characterized in that the aluminate phosphor according to any one of the above-mentioned items 1 to 16 is used as a green phosphor, and the light film has a residual light time of 0 ms or less. The body is a blue glory body, and the afterglow time is 3. Gms or less. (4) The body is a red fluorescent body. (22) The cold cathode fluorescent Ludong xenon lamp described in the above (21), wherein the blue color The phosphor is a live pin for Eu. • About • Limestone for 疋 或 or Eu 赋 镁 • Magnesium aluminate glory body 'The above red phosphor is Eu active oxidation (4) light body or Eu 098124986 14 201011092 Acid strontium phosphor. (23) A backlight unit' characterized by using a glory lamp as described in (19) or (2) above, or a cold cathode fluorescent lamp as described in (21) or (22) above. (24) A liquid crystal display device characterized by using the backlight unit of the above (23) to be pseudo-pulsed. (Effect of the Invention) The aluminate phosphor of the present invention, although the constituent elements constituting the matrix itself are composed of the same constituents as the former phosphors, "but by making the constituent ratios of the constituent elements different from those of the prior homologues , a green luminescence with a higher brightness than the previous substance can be obtained. Further, since the proportion of the relatively inexpensive Al2?3 parent component is high and the proportion of the relatively expensive Tb parent component is low, there is an advantage that the manufacturing cost is reduced. Moreover, in the case where Μη is used as the main green luminescent activating agent (particularly in the case of χ=1), it can be made into a green region illuminating compared to the illuminating in the ultraviolet region which cannot be visually observed and does not contribute to brightness. High intensity. In the phosphor of the present invention, the residual light can be remarkably shortened with respect to the previous green luminescent phosphor. Further, the phosphor of the present invention is in the form of a fluorescent lamp, and a substitute for the phosphoric acid phosphor of the prior Tb is used. Particularly in cold cathode fluorescent lamps, by using the aluminate phosphor of the present invention, a cold cathode fluorescent lamp having a higher beam and higher beam maintenance ratio can be produced. 098124986 15 201011092 In particular, in the case of using a cold cathode fluorescent lamp using the 发光n as a green light-emitting activating device of the present invention, the color reproduction range can be made larger than the previous one. The cold cathode fluorescent lamp that activates the green phosphor of Tb is wider, and can also widen the color reproduction range of TV and the like. Further, the residual light time of the cold cathode lamp can be remarkably shortened, and in particular, it is used for a liquid crystal display device which is intermittently driven, and a liquid crystal display device having a small residual image can be obtained. Further, the aluminate phosphor of the present invention can be applied not only to a cold cathode fluorescent lamp, but also to a vacuum ultraviolet light-emitting element such as a plasma display which is excited by a vacuum ultraviolet region. Further, by appropriately selecting the excitation wavelength of the excitation light source used in combination with the phosphor of the present invention, it can be suitably used for LED or the like. [Embodiment] The aluminate fluorescent system of the present invention has a general formula (CexTU^·y(Mgl_zMnz)〇·nAl2〇3 (however, in the formula, X, y, z, and n are respectively 〇&lt;x&lt;1 When the number of conditions satisfying the condition of 〇6, 8 is satisfied, the aluminate phosphor of the present invention satisfies the number of conditions (1) and 〇i. As shown in the general formula, the degree of exemption is a common feature similar to that of the conventional phosphor. The following is a description of (1) the case where Mn is mainly used as an activator (7) the case where T4Mn is used as an activator, ( 3) It is preferable to use three embodiments as the active agent of Jing 098124986 201011092, and it is possible to extremely shorten the 1/10 afterglow time. (First embodiment of the present invention) The first embodiment of the present invention is suitable. The aluminate phosphor is characterized by the general formula (CexTbkhCb · yCMgi-zMnJO · ηΑ12〇3 (but x=1) - in the formula, y, z and η respectively satisfy 〇.2Sy The number of conditions of $1.8, O.lSzSl, ❹, that is, the aluminate phosphor of the first embodiment of the present invention is important from the previous η 活活钸. The stoichiometric composition of the magnesium aluminate phosphor, the ratio of violent, magnesium, and aluminum, according to the brightness of the green luminescence and the desired chromaticity, the luminescence of the near ultraviolet region and the luminescence of the green region The intensity ratio, etc., such that X, y, 2, and 11 in the above general formula are adjusted within such a range. In addition, the so-called Μ 赋 赋 化学 镁 镁 镁 镁 镁 镁 镁 镁 ( ( ( ( C C C C C C C C Mn is about: : , in the above general formula, y ❹ is 2' z is an arbitrary number 'n value is the aluminate phosphor of the first embodiment of the present invention, and the above chemical 'metering composition phase In comparison, there is a decrease in the total amount of Ce relative to manganese and magnesium: the above-mentioned y (the ratio of the stimuli of the fluorescent towel to the magnesium) is less than 22, and it is difficult to obtain sufficient In other respects, if it exceeds 1.8, the improvement of the illuminance is not achieved close to the previous stoichiometric composition. The preferred range of the y value is 0.3 Sy, .2, more preferably 〇i 2 . z (the ratio of the + in the phosphor), if 098124986 17 201011092 is within the range of Ol^zSl If it is less than oi, Mn is too small and sufficient light emission cannot be obtained. If more light emission is desired, it is preferably 〇2 or more, and particularly preferably 0.4 or more. On the other hand, the Μη is a large part. It is difficult to become a big problem. However, in the case where the chromaticity pursues a darker green (in the case of pursuing a wide range of color reproduction), it is preferably 0.9 or less, and is compatible with NTSC (National Television System Committee). In the case where the coordinates pursue high brightness, the chromaticity of 0.9 or more is optimal. Further, in the aluminate phosphor of the first embodiment of the present invention, η in the above general formula is 7 or more. If the η value (the mixing ratio of Ce203 to Α1ζ〇3 in the phosphor of x=l) is less than 7, the luminance characteristics are liable to lower. In the aluminate phosphor of the first embodiment of the present invention, the amount of Al2〇3 can be increased as compared with the known composition described in Patent Document 1 and the like. When the η value is 12 or more, the shape of the crystal of the phosphor changes from the shape of the flat plate to the thickness and is closer to the shape of the ball. Therefore, in the case of forming a fluorescent film such as a lamp, the activity in the coating medium is easily matched with other flickers. It is difficult for the light body to have a color difference of 0 in the tube end, and the filling property is also excellent, and it is easy to obtain a sufficient amount of light as a lamp. On the other hand, if it exceeds 40, the luminance gradually decreases. Therefore, as the η value, 12$η$40 is preferable, and 12SnS30 is more preferable, and ι2^η^20 is particularly preferable. Further, the crystal salt phosphor according to the first embodiment of the present invention may contain other elements in the composition sheet without greatly deviating from the effects of the present invention, and examples of the composition include Mg in the composition. In the range that does not greatly hinder the effects of the present invention, it is also possible to replace the Mg with an ionic radius close to, for example, a divalent metal such as 098124986 18 201011092, and Ce is the same as Υ, Gd, A small amount of substitution such as La may also be possible, and a part of Α1 may also be replaced by Ga and/or Sc. In addition, the composition of the aluminate phosphor of the first embodiment of the present invention can be confirmed by ICP luminescence (Inductively Coupled Plasma). In the aluminate phosphor according to the first embodiment of the present invention, since the composition is significantly different from that of the first stoichiometric composition, the crystal structure is estimated to be changed. However, the details are not known, but The preliminary measurement is contracted in the a-axis direction and extends in the c-axis direction compared to the previous stoichiometric composition. That is, in the J. Electrochem. Soc. SOLID-STATE SCIENCE AND TECHNOLOGY MAY 1976 Vol. 123 No. 5 P691, the a-axis of CeMgA1ii〇i9 (=Ce203 · 2(Mg)0 · llAl2〇3) is 5.61. The nm and c Φ axes are ai^nm'CeMnAluOWCeA · 2(Mn)〇·11A1203), the a-axis is 5.62 nm, the c-axis is 21-96 nm, and the c-axis length/a-axis length is 3 92 or less. In contrast, in the phosphor structure in which n is 12 or more in the present invention, the a-axis is 5.58 nm or less, the c-axis is 22.00 nm or more, and the c-axis length/a-axis length is 3.93 or more, particularly preferably c. The shaft length / a-axis length is 3.94 or more. As a characteristic aspect of the aluminate glaze according to the first embodiment of the present invention, it is preferable that the ratio of the luminescence intensity at 350 nm to the luminescence intensity at 518 nm is less than 15%. Since the luminous intensity of the usual stoichiometric composition is 098124986 19 201011092, the ratio is 20% strong. Therefore, it is known that the etched glory of the present invention can efficiently transfer energy from Ce to Μη. Below, use the data description. In the sulphate phosphor of the first embodiment of the present invention, as shown in the table, when (^^, and then set to a certain amount, the ultraviolet ray having a wavelength of 254 nm is excited in the case where the amount of enthalpy is changed. The change in the luminous intensity (♦) of the luster wavelength of 5i8 nm and the luminous intensity (▲) of the luminous intensity of 35 Gnm is shown in Fig. 1(A). In addition, in the table, y, & z represent the above general formula ❹ (CexTbhW· y(Mgl.zMnz)0 · ηΑι2〇3 (but χ=1) The values of y and z, and the values other than y and z are the number of moles of each constituent element. The data of A) is the ratio of the intensity of the light emission of the light-emitting wavelength of 518 nm with respect to the change of the amount of Mg to the light-emitting wavelength of 35〇11111, which is not the same as FIG. 1(B). In addition, in FIGS. 1(A) and (B) In each of the graphs, the χ axis represents the y value in the above general formula (CexTbi-xLOs · y(Mgi_zMnz)0 · ηΑ12〇3 (but χ=ι), because the so-called chemical composition is Μη The amount is 〇21 mol, and the amount of Mg is 0.79 mol. In the above general formula, y=2, z=〇21, n=11, ie,

Ce203 · 2 (Mn〇.21Mg〇.79) 0 · llAl2〇3 of the acid salt phosphor. As can be seen from Fig. 1 (A) and (B), when the stoichiometric composition (y = 2. 〇) is shifted in the direction of decreasing y, the luminescence intensity from the near ultraviolet region of Ce is relative to that from Μη. The luminous intensity of the green light region is significantly increased. [Table 1] 098124986 20 201011092

Ce 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Mg 0.12 0.18 0.24 0.29 0.35 0.46 0.59 0.71 0.82 0.94 1.06 1.18 Μη 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 A1 12.9 12.9 12.9 12.9 12.9 12.9 12.9 12.9 12.9 12.9 12.9 12.9 y 0.66 0.78 0.90 1.00 1.12 1.34 1.60 1.84 2.06 2.30 2.54 2.78 z 0.64 ^54 0.47 0.42 0.37 0.31 0.26 0.23 0.20 0.18 0.17 0.15 Further, the aluminate phosphor of the first embodiment of the present invention is compared with the prior art. The stoichiometric composition material not only improves the above-described energy transfer from Ce to Μη but also improves the absorption of mercury luminescence. Figure 2 shows this situation. The stoichiometric composition of the previous phosphor, in the range of VUV (Vacuum Ultra_Violet light, vacuum ultraviolet light) (172 nm), the luminescence of the mercury ray (mainly 254 nm) also shows approximately the same degree of excitation spectral intensity 'relatively, by stoichiometry In the phosphor of the present invention in which the composition (y = 2. 〇) is shifted in the direction of decreasing y, it is known that the excitation by the mercury ray is nearly twice as high as the excitation of ν υ ν. The method for producing an aluminate phosphor according to the first embodiment of the present invention is not particularly limited as long as it is a method generally used for producing a phosphor. It is preferable that the Ce compound, the Mg compound, the]Vin compound, and the A1 compound are stoichiometrically made to have a composition ratio of Ce, Mg, Μ, and A1 to that of the phosphoric acid of the first embodiment. The composition ratio is - mixed, and satin can be burned. More preferably, a Ce compound which can be converted into an oxide of cerium (Ce) by heating, and a Mg compound which can be converted into an oxide of magnesium (Mg) by heating can be converted into an oxide of manganese (Mn) by heating. The Μ 化合物 compound and the ruthenium 1 compound which can be converted into an oxide of 绍 1 are mixed and calcined. The phosphor raw material which is preferably used in the present invention may be exemplified by carbonic acid, oxidized 098124986 21 201011092 strontium, magnesium carbonate, magnesium oxide, manganese carbonate, manganese oxide, aluminum oxide, etc., and others which can be easily converted into oxides by strong heat. salt. The specific production method of the aluminate phosphor of the first embodiment of the present invention is carried out, for example, in the following procedure. (1) The above-mentioned raw materials are weighed in a specified amount, and thoroughly mixed by a mixing means using a ball mill or a V-type mixer. (2) Filling the obtained mixture into a heat container such as alumina crucible, which is also included in a high-temperature furnace, and is heated in a reducing atmosphere to a temperature of 1400 to 160 CTC, and the time required for cooling is simmered for 1 to 26 hours. . (3) The calcined material to be applied is subjected to various treatments such as dispersing, washing, and drying in the same manner as in the subsequent processing of the conventional phosphor. In the present invention, in the mixture of the phosphor raw material compound to be calcined, in the same manner as in the case of obtaining a known aluminate phosphor, in order to promote the reaction, a fluoride such as aluminum fluoride or boric acid and oxidation may be added. Boron or the like acts as a flux. The particle size of the woven salt phosphor of the first embodiment of the present invention is not particularly limited, but in the case of being applied to the cold smolder light &lt; camping film of the present invention, the degree of operation and In terms of color uniformity, the fsss particle size may be arbitrarily selected from the range of about 1 to 20, preferably 2 to 8, more preferably 2 to 7. The fluorescent lamp of the present invention is used in addition to the treatment. The salt-reducing phosphor of the invention is produced as a fluorescent film in the same manner as the conventional fluorescent lamp. The same is true for cold cathode fluorescent lamps (including external electrode type). 098124986 22 201011092 In other words, the aluminate phosphor of the first embodiment of the present invention is simultaneously added to water or a binder such as a low-melting glass powder, a fine particle metal oxide, or a fine metal borate or phosphate. The solvent is coated in a solvent such as butyl acetate or isopropyl alcohol to prepare a phosphor coating paste, which is applied to the inner wall of the glass tube and dried to form a fluorescent film, which is baked and then sealed with mercury. Reduce-pressure, seal, and assemble the electrode. Of course, it is obvious that the phosphor of other colors can be mixed with white for use. The aluminate phosphor of the first embodiment of the present invention and the fluorescent lamp using the same are preferably used for general illumination, and the color reproduction range is compared with the prior cold cathode fluorescent lamp (usually A BAM phosphor is used as the blue color, [Αρ phosphor is used as the green, and γ〇χ (yttria) phosphor is used as the red color), and a wide range can be reproduced. In the case where the phosphor of the present invention is used as a fluorescent lamp for illumination, a blue and red phosphor is mixed to emit white light for use. At this time, the phosphor used can be used in combination with the previous LAP phosphor. For example, as a blue illuminator, Eu-activated BAM or SCA labor light body can be used. When a lamp for illumination is used, a substance having a wide half-value width of the luminescence spectrum is suitable for use. Therefore, for example, if it is bam, it is suitable to use Mn and Sr, and if it is SCA, it is suitable to use suitably to change the amount of Sr, Ba, ca, and 4. Also 'red is Y2〇3: Eu and γ(ρ, V〇)4:Eu, etc. are suitable for use, and in which as needed (for example, for meat lighting) 'add 3.5MgO · 0.5MgF2 · Ge〇2 : Μη, etc. as the deep red firefly 098124986 23 201011092 light body is also good. Of course, the phosphor of the present invention can also be used as a rare gas lamp that does not excite mercury. In this case, BAM, Y(P, V0)4: Eu, etc. can be appropriately selected in a vacuum when appropriately combined in white. A substance that emits light sufficiently under ultraviolet light. On the other hand, when the phosphor of the present invention is used in a CCFL-like lamp for displaying an image, it can exhibit a deeper color than the previous LAp phosphor, and thus a wide-color reproduction range is produced. The lamp is better. Thus, for example, a forest or the like, which is slightly yellowish green compared to the previous LAP, can be expressed in a more realistic green form. In this case, the phosphors to be combined are in the form of CCFL, and the phosphors used in combination with BNA in combination with Μη are suitable for use. For example, as a blue phosphor, a 丫 value of less than 〇〇7 can be suitably used. Bam phosphor 'or s value is less than 0 04 〇 SCa, etc., as a red phosphor, Y203:Eu and Y(P,VO)4:Eu, etc., particularly preferably γν〇4 :

Eu. The phosphor of the present invention can be used in combination with a backlight element for a liquid crystal display device. Further, a liquid crystal display device using the phosphor of the present invention can achieve a wide color reproduction range. In this case, a suitable camping body used in combination with the aluminate phosphor of the first embodiment of the present invention from the viewpoint of widening the color reproduction range is a BAM phosphor which is Eu-activated in the case of blue. Or an SCA phosphor having a y value of 〇〇4 or less, and a red γοχ or VY〇4 phosphor is preferred. Further, even if it is used as a phosphor for LED, it can be used by appropriately selecting the excitation wavelength. (Second embodiment of the present invention) 098124986 24 201011092 A sulphate phosphor suitable for the second embodiment of the present invention is a general formula (CexTbl-x) 2 〇 3 · ^ (la-push 2 〇· ηΑ12〇3 (however, in the formula, x, y, z, and η are each an aluminate phosphor represented by the number of 〇&lt;χ&lt;1, 〇). Further, the sulphate glaze of the embodiment of the present invention 2 may contain other elements in its composition without greatly deviating from the effects of the present invention, and specific examples include Mg and Mn, and In the same manner as the aluminate phosphor of the first embodiment, the ionic radius of the 馗§ and Mn# is close to the extent that the effect of the aluminate phosphor of the second embodiment of the present invention is not greatly impaired. For example, a divalent metal such as Sr and Ba may be substituted in a small amount, and 'C' may be substituted by a small amount such as γ, Gd or La, and a part of A1 may be substituted by Ga and/or Sc. The aluminate phosphor suitable for the second embodiment of the present invention has a stoichiometric composition of (Ce+Tb) compared to the previous CAT: Μn phosphor: ❹(Mg + Mn) The total molar ratio is about 1:1 composition, with the basis of the green illuminance and the desired color chromaticity (to the total molar of Ce + Tb): (Mg + Μ total molar) Staggered into 2: 0.6~1.8 composition of the features. In addition, the stoichiometric composition of the former CAT: Μη phosphor is in the general formula where X is an arbitrary number, the y value is 2, and the ζ value is 〇&lt;ζ$ι, η is 1 in the general formula. x (Ce replaces the ratio of Tb in the phosphor), if it is appropriately selected within the range of 〇&lt;χ&lt;1, on the phosphor for obtaining higher brightness, 098124986 25 201011092 0.5SxS0.9 It is better. In the general formula y (the ratio of the sum of Ce203 and Tb203 in the phosphor to (Mg + Μη)), if it is less than 0.6, it is difficult to obtain sufficient luminescence. On the other hand, if it exceeds 1.8, it becomes close to the previous stoichiometric composition, and the improvement of the brightness of the luminescence cannot be achieved. The preferred range of y values is 〇.8Sx, xS1.6, more preferably 1.1 Sy, 1.6. In the general formula, z (the ratio of Μ in Mg + Mn in the phosphor) is within the range of O^zSl, and can be appropriately selected to obtain desired chromaticity and brightness, but by chromaticity point and brightness In terms of OSzS0.2, it is better. The best is z=0. When z = 0, that is, a phosphor having no Μη, the selection range of the chromaticity point is narrowed, and the chromaticity point can be adjusted by, for example, appropriately mixing with the phosphor of the first embodiment of the present invention. Further, in the general formula, η (the ratio of the total of Ce203 to Tb203 in the phosphor to Al2〇3) is 7 or more. As described above, in the phosphor of the present invention, the amount of Al2〇3 can be increased. On the other hand, if the value of η is less than 7, the brightness characteristic is deteriorated, which is not preferable. When the η value is 11 or more, the crystal shape is rounded, and since the film quality at the time of coating can be easily improved, it is preferable, and if it exceeds 20, the brightness starts to decrease, so that the luminescence brightness is η. A value of ll$nS20 is preferred. The aluminate phosphor of the second embodiment of the present invention is not particularly limited as long as it is a method for producing a phosphor in the same manner as the phosphor of the first embodiment. Preferably, the Ce compound, the Tb compound, the Mg compound, the 098124986 26 201011092 Μη compound, and the A1 compound are stoichiometrically made to have a composition ratio of Ce, Tb, Μη, and A1 and the aluminate of the second embodiment. The composition ratio of the phosphor is uniformly mixed, and calcination is sufficient. More preferably, (i) cerium oxide, or cerium carbonate, cerium nitrate or the like, a Ce compound which can be converted into an oxygen compound of cerium (Ce) by heating, (ii) cerium oxide, or cerium carbonate, cerium nitrate, cerium chloride A Mg compound which can be converted into an oxide of magnesium (Mg) by heating, such as a Tb compound which is heated to become an oxide of cerium (Tb), or a magnesium compound such as magnesium oxide or magnesium carbonate which is heated to become an oxide of magnesium (Mg) A general formula of a stoichiometric composition of aluminum, or sulphate or the like which can be converted into an oxide of aluminum (A1) by heating is: (CexTbi-xhOs yiMgi.zMriz^O · ηΑ12〇3 (however, In the middle, χ, y, ζ and η are respectively mixed in a ratio satisfying the conditions of 0$χ&lt;1, O.gym 〇&lt;d, 〜, and calcination. The second embodiment of the present invention The specific production method of the aluminate phosphor is carried out, for example, in the following procedure: (1) The raw materials are weighed as specified in the above-mentioned materials and thoroughly mixed by a mixing means such as a ball mill or a v-type mixer. Filling the obtained mixture into a heat-resistant container such as alumina crucible, and reducing the ambient gas to 1400 to 160 〇ec, The time required for the furnace to be raised and lowered in a high-temperature furnace is simmered for 1 〇 to 26 hours. (3) For the obtained saki, the application of the conventional fluorination is applied to the dispersion and washing of the sample. In the present invention, in the mixture of the phosphor raw material compound for calcination, 098124986 27 201011092 may be added in order to promote the reaction, similarly to the case of obtaining a known aluminate phosphor. Fluoride such as aluminum fluoride, boric acid, boron oxide, or the like is used as a flux. The particle size of the aluminate phosphor according to the second embodiment of the present invention is not particularly limited, but is applied to the present invention. In the case of a fluorescent film or a fluorescent film of a cold cathode fluorescent lamp, the FSSS particle size may be arbitrarily selected from the range of about 1 to 20 in terms of the degree of operation and color uniformity, and is preferably 2 to 8. The fluorescent lamp and the cold cathode fluorescent lamp of the present invention are the same as the prior art cold cathode fluorescent lamp except that the aluminate phosphor of the present invention thus obtained is used as a fluorescent film (of course, an external electrode type is also included. The so-called EEFL) processing manufacturing. The aluminate phosphor according to the second embodiment of the present invention may be, for example, a low-melting glass powder, a fine particle metal oxide, or a fine particle metal borate or phosphate, together with a phosphor of another color. The adhesive is simultaneously suspended in water or a solvent such as butyl acetate or isopropyl alcohol to prepare a phosphor coating paste, which is applied to the inner wall of the glass tube and dried to form a firefly, which is then baked. After that, the mercury is sealed, decompressed, sealed, and the electrode is assembled. The aluminate phosphor of the second embodiment of the present invention and the fluorescent lamp using the same are preferably used for general illumination, and further, Color reproduction mode is better than previous cold cathode fluorescent lamps (usually, using BAM phosphors as blue, LAp phosphors as green, and YOX (yttria) phosphors as red), which can reproduce a wide range . Therefore, it is possible to obtain a wide color reproduction range by using the phosphor of the present invention as a liquid crystal display device by using the backlight member for mounting a liquid crystal display device. 098124986 28 201011092 Further, even if it is used as a phosphor for LED, it can be used by appropriately selecting the excitation wavelength. (Third embodiment of the present invention) The third embodiment of the present invention is based on the composition having the excellent characteristics of 1/10 afterglow, in the composition of the second embodiment of the present invention. This is an effect that cannot be obtained by a phosphor having a normal stoichiometric composition, and therefore, it will be described in detail in the third embodiment.铝 The aluminate phosphor of the third aspect of the present invention is characterized in that the phosphor composed of at least ce, Tb, Mg, A1 and ytterbium is characterized by a 1/1 〇 afterglow time of 6 4 ms or less. Aluminate phosphor. Further, the term "constituted" as used in the specification of the present invention is not limited to the third embodiment of the cancer-like portion, and includes substances containing other substances insofar as it does not greatly impair the effects of the present invention. If the i/io afterglow time is longer than 6.4 ms', it is not significantly different from the previous product, and is not suitable for LCD backlights requiring a short afterglow time, and is preferably 6 〇ms or less, more preferably 5.7 ms or less. The third embodiment of the present invention is characterized in that the phosphor of the cancer is a phosphor composed of at least Ce, Tb, Mg, and A1 &amp; 0, and the residual light time of 1/1 为 is 6.4 ms or less. The substance 'its composition is not particularly limited. Preferably, it is a general formula (CexTbi-xLC^ · yCMgiJVlndO · ηΑ12〇3 (however, χ, yz and η are the numbers satisfying the conditions of 〇68 $ 0.95, 0.6Sy$ 1 g, z=〇, 7gn, respectively). The phosphor shown in the above. 098124986 29 201011092 In addition, the phosphor of the general formula * can not be greatly deviated from the scope of the present invention, and can also contain other elements in its group, if enumerated In the specific example, as for the % and Mn', as in the above-described h-form, a small amount of divalent metal such as Sf and ^, which is close to the ionic radius, is close to % and Μ in a range which does not greatly impair the effect of the present invention. It is also possible to substitute, and Ce is similarly substituted with a small amount of Y, Gd, La, etc., and some of the ruthenium may be substituted by Ga and/or Sc. The aluminate phosphor shown in the above general formula is compared. The preferred composition of the previous CAT fluorescene body is Ce/Tb=2 〇 or stoichiometric composition (Ce +

Tb) 1.0纟' has a ratio of Ce to Tb according to the brightness of the green light and the desired afterglow time (in the above formula, χ/(ι_χ) ratio) or (ce +

The ratio of Tb) to Mg (the y value in the above formula) is staggered. In the aluminate phosphor of the third embodiment of the present invention, the content ratio of each of the metal elements constituting the phosphor is shifted from the composition and the stoichiometric composition of the conventional CAT phosphor, and this is staggered ( The indefinite ratio causes a change in the crystal structure of the fluorescent body and a change in the optical property (afterglow characteristic), and it is presumed that a phosphor having various excellent characteristics can be obtained. Further, the stoichiometric composition of the prior CAT phosphor means that X in the general formula is an arbitrary number, the y value is 2' z value is 0, and the η value is 11. In the general formula, 1-χ (instead of the Tb ratio of Ce in the phosphor) becomes smaller, the phosphor brightness tends to decrease, but by shortening the residual light, the start time of the luminance is shortened. It is beneficial to brightness. However, if 098124986 30 201011092 l-x is less than 0.05, that is, when x is more than 〇95, the Tb light emission (green light emission) is excessively lowered, and the brightness of the entire phosphor is reduced. On the other hand, if the 1-x value is 0.32 or more, i.e., xO.68, the composition is close to the previous one, and the reduction of the afterglow time cannot be achieved. Therefore, the preferred X value range is 0.68SxS0.95, and the better value of the X value is 0.7^xS0.85. If the balance between the brightness and the brightness is considered, it is more preferably 0.7$χ$0·75. The afterglow time characteristic is ❹ 0.75$χ$0.85. In the phosphor, the amount of Ce is reduced relative to the amount of Tb (that is, the X value in the general formula is 〇.68 or more), and the afterglow time can be shortened, and by starting the fast effect, χ=0·95 or so It can maintain approximately the same brightness as the previous material. Further, since the proportion of the relatively expensive 2Tb in the matrix component is low, the manufacturing cost can be reduced.

In the general formula, the y value (in the phosphor, the ratio of the sum of 2〇3 and several 2〇3 to MgO) is less than ,6, the afterglow time becomes shorter, and it is difficult to obtain sufficient light-emitting n-plane. 'If it exceeds 18, it will also reduce the brightness. The preferred range of υ is 0.69a 8, more preferably 〇虹...6. As the amount of Ce relative to Tb in the phosphor decreases, (Ce + Tb) decreases with respect to the amount of Mg, and the afterglow time can be greatly shortened. The value of η in the general formula (% of the phosphor in the phosphor and the sum of the chemical

The ratio of Al2〇3 is 7 or more. If the value of n is less than 7, the luminance characteristic is lowered, which is not preferable. 098124986 31 201011092 Moreover, when the η value is u or more, the crystal shape is rounded, and since the film quality of the fluorescent film at the time of coating can be easily improved, the brightness is preferably lowered if it exceeds 3 〇'. 'Therefore, the lower limit value of the η value is 11 or more, and the upper limit is preferably 3 Å or less, more preferably 2 Å or less. Of course, the preferred afterglow time of the phosphor shown in this general formula is 64 ms or less. If the 1/10 afterglow time is longer than 6.4 ms, it is not suitable for LCD backlights requiring short afterglow, and is preferably 6 〇ms or less, more preferably "below". The third embodiment of the present invention is acid. The salt phosphor is also the same as the β-stacted phosphor, and the method used in the usual production of the glare is not particularly limited. Preferably, the Ce compound, the Tb compound, the % compound, and the ruthenium are used. The compound is stoichiometrically mixed with the composition ratio of Tb, 岣, and ai in accordance with the composition ratio of the pure salt phosphor of the third embodiment, and calcined. More preferably, (i a chromic oxide, or a zinc carbonate, a cerium nitrate or the like, a Ce compound which can be converted into an oxide of cerium (Ce), (ii) cerium oxide- or a reversed, a nitric acid test, a chlorination series or the like can be converted into a test by heating ( The Tb compound of the oxide, (IV) magnesium oxide, or magnesium carbonate, etc., which can be converted into an oxide of the town (Mg) by heating, and (iv) oxidized or sulphuric acid, etc. 1) The oxide ❺A1 compound, which has the stoichiometric composition formula: ^χΤνχ)2〇3 · y(Mgi zMn z)〇·福2〇3 (However, in the formula, X, ^, z, and 11 are the numbers satisfying the conditions of 0 68$χ^〇.95, 0.6$ym z=〇, 7^η 098124986 32 201011092, respectively. The method of producing the aluminate phosphor according to the third embodiment of the present invention is the aluminate phosphor of the first and second embodiments of the present invention. The manufacturing method is similarly carried out, for example, by the following procedure: - (1) The above-mentioned raw material #amount specified amount is sufficiently mixed by a mixing means such as a ball mill or a v-type mixer. (2) The obtained mixture is obtained. Filled into a heat-resistant container such as alumina crucible, and immersed in a reducing atmosphere for 14 〇〇 to w 〇 (Tc ' is also included in the time required for the furnace to rise and fall in a high-temperature furnace, and calcined for 10 to 26 hours. (3) The obtained calcined product is subjected to various treatments which are similarly dispersed, washed, and dried after the application of the usual phosphor, and in the present invention, in the mixture of the phosphor raw material compound for the calcination, In the same manner as in the case of obtaining a known aluminate phosphor, in order to promote the reaction, it is also possible to add Fluoride, such as gasification, or boric acid, boron oxide, etc. as a refining agent. 10 The particle size of the aluminate phosphor according to the third embodiment of the present invention is not particularly limited, but is applied to the present invention. In the case of the fluorescent film 4 of the fluorescent lamp of the invention and the cold cathode fluorescent lamp, it is preferable that the FSSS particle size is about 1 to 20 in terms of the degree of operation and color uniformity, and preferably. 2 to 8. The fluorescent lamp or the cold cathode fluorescent lamp of the present invention is the same as the fluorescent lamp and the cold cathode fluorescent lamp except the aluminate phosphor of the present invention obtained by the treatment. Lamp processing manufacturing. That is, the aluminate phosphor of the present invention is optionally combined with other color phosphors 098124986 33 201011092, for example, low melting glass powder, particulate metal oxide, or particulate metal borate or The adhesive such as phosphate is simultaneously suspended in a solvent such as water or an organic solvent such as butyl acetate or isopropyl alcohol to prepare a phosphor coating paste. The obtained dope is applied to the inner wall of the glass tube to form a fluorescent film by drying with warm air or the like, and then baked, followed by mercury sealing, decompression, sealing, and assembly of the electrode. In the cold cathode fluorescent lamp of the present invention, the phosphoric acid phosphor of the third embodiment of the present invention described above is used as a green glare, and the _1/10 afterglow time is blue or less. A mixed phosphor which is a color phosphor and a red phosphor having a residual light time of 3.0 ms or less is preferably used as a fluorescent film. A blue glory body having a 1/10 afterglow time of 10 ms or less can be cited.

Eu Fu Shi Lu _ ash stone phosphor (hereinafter also referred to as SCA phosphor), BAM phosphor, etc., wherein the SCA glory body can be suitably used.

The moiré phosphor having a moier time of 3 Gms or less may be a yox phosphor, an Eu-activated phosphor (hereinafter also referred to as a γν phosphor), and γ 〇χ 适当 may be suitably used. Light body. According to the third aspect of the present invention, the reduced-salt sputum has a characteristic of a short period of 1/10 of the residual time. Therefore, when the polychromatic light body combined with the above is appropriately selected, the residual light can be used as the _(four) lamp. It is possible to obtain a short-lasting backlight element 'or by intermittent lighting' to obtain a dynamic liquid crystal display device. — 098124986 34 201011092 In the phosphors of this month, in the phosphors of all the embodiments, inorganic compounds and organic compounds can be used for the purpose of suppressing the deterioration of brightness and improving the life characteristics. The coated material is coated on the surface of the treated phosphor. The method of the coating treatment is not particularly limited. For example, a method in which the fine particle coating material ' is mixed with the coated phosphor, and dried and adhered; and the coating material is deposited on the surface of the coated phosphor to be adjusted. Method such as PH. © A method of adhering to the surface of the coated phosphor by a potential; or a method of additionally mixing and coating the material as a binder, and arbitrarily selecting according to the characteristics of the coated glare and the substance to be coated. Specific examples of the coating material include carbonates such as oxidized towns, oxidized rots, and oxidized materials, such as oxidized H-based metal carbons and rare earth metal carbonates; and hydroxides of hydroxides. Among them, the carbonate of the rare earth metal described in Japanese Patent No. (4) is coated, and it is preferable to use it as a lamp to improve the life. The carbonate of the rare earth metal is preferably carbonated or strontium carbonate, and the coating amount thereof is preferably 0.05 to 5% by weight based on the weight of the phosphor, and more preferably 5% by weight. [Examples] Hereinafter, the present invention will be described in more detail with reference to the preferred embodiments, however, the invention should not be construed as limited. (Example according to the first embodiment of the present invention) 098124986 35 201011092 [Review of y value and z value 1 : a ratio change of Mg content when Μη and A1 are constant] 镁 and 绍 are a certain amount of magnesium Change, review the improvement of luminous brightness. [Example 5] • Ce203: 1.00 Mohr • MgC03 : 0.47 Mohr • Μ 02 02 : 0.42 Mo Er • Α 1203 (α type): 12.94 Mo Er • A1F3 : 0.02 Mo 彳 将 Mix the above materials thoroughly and fill them into 坩埚Then, the lead block is placed on the phosphor material, and is capped and calcined in a nitrogen atmosphere containing water vapor at a temperature of 1550 ° C for 24 hours. Next, the calcined powder is dispersed, washed, dried, and sieved to obtain a composition formula of Ce2〇3 · 〇.42MnO · 〇.47MgO · 12 9Al2 〇 3 "that is, 'Ce2 〇 3 * 0_89 (Mn0 .47, Mg0.53) Mn· ΠΑΛΙΟ 〗 》 Mn2+ © activating aluminate phosphor. In addition, AIR is a co-solvent commonly used in the manufacture of phosphors. The luminosity and brightness of the obtained phosphor are shown in Table 2. Further, in Table 2, Al2〇3襕 represents the η value, the Mg + Mn column represents the y value, and the Mn/(Mg + Μη) shed represents the z value. In addition, a color luminance meter (manufactured by K〇nica Minolta Co., Ltd.: CS200) was used as a commercially available yttrium phosphate phosphor (Chemical 098124986 36 201011092 manufactured by Optonix Co., Ltd.: phosphor LP-) G2) The brightness as a standard is regarded as 100, and the brightness is measured.

098124986 37 201011092 [Table 2] CC2〇3 MgO MnO AI2O3 Mg+Mn Mn/(Mg+Mn) Color brightness η yz X y Brightness FSSS Example-1 1 0.00 0.42 12.9 0.42 1.00 0.187 0.604 87 Example-2 1 0.12 0.42 12.9 0.54 0.78 0.187 0.631 88 Example-3 1 0.24 0.42 12.9 0.66 0.64 0.172 0.666 87 Example 4 1 0.35 0.42 12.9 0.78 0.55 0.173 0.720 91 Example-5 1 0.47 0.42 12.9 0.89 0.47 0.173 0.746 93 Example-6 1 0.59 0.42 12.9 1.01 0.42 0.172 0.765 92 Example-7 1 0.71 0.42 12.9 1.13 0.37 0.171 0.763 89 Example-8 1 0.71 0.42 12.9 1.13 0.37 0.171 0.777 87 Example-9 1 0.82 0.42 12.9 1.25 0.34 0.169 0.770 86 Example -10 1 0.92 0.42 12.9 1.34 0.32 0.169 0.775 82 Example-11 1 1.06 0.42 12.9 1.48 0.29 0.168 0.762 80 Example-12 1 1.18 0.42 12.9 1.60 0.26 0.167 0.764 72 Comparative Example-1 1 1.41 0.42 12.9 1.84 0.23 0.168 0.765 49 Comparative Example-2 1 1.65 0.42 12.9 2.07 0.20 0.166 0.764 49 Comparative Example-3 1 1.88 0.42 12.9 2.31 0.18 0.162 0.770 48 Comparative Example *4 1 2.12 0.42 12.9 2.54 0.17 0.164 0.7 57 49 Comparative Example-5 1 2.35 0.42 12.9 2.78 0.15 0.161 0.735 48 Example-13 1 0.00 0.80 13.0 0.80 1.00 0.210 0.717 102 Example-14 1 0.92 0.31 12.9 1.22 0.25 0.164 0.759 77 Example-15 1 0.92 0.35 12.9 1.27 0.28 0.166 0.756 80 Example-16 1 0.92 0.42 12.9 1.34 0.32 0.168 0.775 84 Example-17 1 0.92 0.49 12.9 1.41 0.35 0.169 0.760 82 Example-18 1 0.92 0.56 12.9 1.48 0.38 0.171 0.780 82 Example-19 1 0.92 0.64 12.9 1.55 0.41 0.176 0,785 75 Example-20 1 0.92 0.71 12.9 1.62 0.43 0.180 0.781 62 Example-21 1 0.58 0.42 8.0 1.00 0.42 0.170 0.740 75 Example-22 1 0.58 0.42 9.0 1.00 0.42 0.171 0.739 84 4.7 Example-23 1 0.58 0.42 12.0 1.00 0.42 0.176 0.730 92 4.2 Example-24 1 0.58 0.42 13.0 1.00 0.42 0.185 0.721 91 3.5 Example-25 1 0.58 0.42 14.0 LOO 0.42 0.185 0.725 92 3.4 Example -26 r 1 0.58 0.42 16.0 1.00 0.42 0.183 0.722 93 3.0 Example-27 1 0.58 0.42 20.0 1.00 0.42 0.182 0.719 91 2.9 Example-28 1 0.58 0.42 25.0 1.00 0.42 0.182 0.722 90 3.1 Real Example -29 1 0.58 0.42 33.0 1.00 0.42 0.181 0.721 80 [Examples 1 to 4, 6 to 12, and Comparative Examples 1 to 5] In the same manner as in the above Example 5 except that the composition shown in Table 2 was used, 38 was taken. 098124986 201011092 The chromaticity and brightness of each of the obtained phosphors are shown in Examples 1 to 4' 6 to 12 and Comparative Example 1, 6 Mn2+, and the results are shown in Table 2. Based on the brightness of the y value change, and in the figure. ', _ 3 [Review of y value and z value 2 : Mn content when Mg and A1 are constant | change] ❹ Magnesium and aluminum change the amount of manganese when necessary, and review the improvement of luminescence brightness [Examples 14 to 20 ] ^ ° In addition to the composition shown in Table 2, the Mn2+-activated aluminate phosphors of Examples 14 to 20 were obtained in the same manner as in the above Examples.叟, so the chromaticity and brightness of each of the obtained phosphors are shown in Table 2. [The review of η value: the ratio of the A1 amount of Μη and Mg is constant and the change of magnesium to -the timing, Improvement of Luminance Brightness] β [Examples 21 to 29] ^ ° In addition to the compositions shown in Table 2, the above-mentioned Example 5 - Examples 2 to 29 were obtained as the ?n2+-activated aluminate phosphors. Here, the chromaticity and brightness of each of the obtained phosphors and the average particle diameter by the FSSS method are combined and shown in Table 2. Further, based on the results of Table 2, the degree of cloth accompanying the change in the amount of Ai is shown in Fig. 4. In Fig. 4, the horizontal axis is 11 (yttrium oxide in the phosphor). Further, regarding Examples 22 to 28, based on the results of Table 2, the particle size accompanying the change in the amount of 098124986 201011092 A1 is shown in the graph of Fig. 5. In Fig. 5, the horizontal axis represents the amount of A1 (mole) in the phosphor. [Review of Mg amount] [Example 13] The Mn2+ activating aluminate phosphor of Example 13 was obtained by the same treatment as in Example 5 except that the composition shown in Table 2 was used. The chromaticity and brightness of the obtained phosphors are shown in Table 2. As in the above, all of Examples 1 to 29 exhibited green light emission of higher brightness than Comparative Examples 1 to 5. Further, from the results of Examples 22 to 28, it is understood that when the amount of a1203 is increased, the average particle diameter tends to be small. (Examples corresponding to the second embodiment of the present invention) [CAT phosphor] [Examples 30 to 37, 70, and Comparative Examples 6 and 7] Six kinds of raw materials (Ce02, Tb407, MgC03, Αΐ2〇3) α type), Η3Β〇3, and A1F3) are fully filled with the composition shown in Table 3, and then filled to the crucible, and then placed on the phosphor material, and sealed with nitrogen gas atmosphere containing water vapor. In the middle temperature, the maximum temperature of 155 CTC contains the temperature rise and fall time for 24 hours of calcination. Η3Β〇3 and A1F3 in the raw materials are the co-solvents commonly used in the manufacture of phosphors. Next, the calcined powder was subjected to dispersion, washing, drying, and sieving treatment. In Examples 30 to 37, 70 and Comparative Examples 6 and 7, Tb was revitalized with 129124986 40 201011092. In addition, the composition was confirmed by ICP. The luminescent color (chromaticity), the relative luminance, and the average particle diameter measured by the FSSS method (Fisher Subsieve Size) of each of the obtained phosphors are shown in Table 3. In addition, in the measurement of chromaticity, a color luminance meter (trade name "CS200" manufactured by Konica-Minolta Co., Ltd.) was used. 0Pt〇nix company product 0, 'LP-G2') When the brightness of the standard product is regarded as 100, the phosphors of the respective examples are measured in the same manner as 'relative values'. [Table 3] Phosphor composition Luminous color (chroma) Relative brightness FSSS [X] [y] m Particle size Example 30 (Ce〇.67, Tb〇, 33) 2〇3 · l-8MgO · 13Α12〇3 0.338 0.596 102 4.7 Example 31 ( Ce〇.67, Tb〇.33) 2〇3 · 1.6MgO · 13Al2〇3 0.338 0.598 102 5.4 Example 321 (Ce〇.67, Tb〇, 33) 2〇3 . 1.4MgO · IIAI2O3 0.340 0.597 104 7.1 Example 331 (Ce〇.67, Tb〇.33) 2〇3 · 1.4MgO · 13AI2〇3 0.337 0.600 105 5.5 Example 341 (Ce〇.67, Tb〇.33) 2〇3 · 1.2MgO · ΠΑΙ2Ο3 0.338 0.603 106 5.8 Example 35 (Ce〇.67, Tb〇.33) 2〇3 · MgO · IIAI2O3 0.340 0.592 100 6.3 Example 36 (Ce〇.67, Tb〇.33) 2〇3 · MgO · 13Al2 〇3 0.340 0.597 101 6.3 Example 37 (Ce〇.67jTb〇.33) 2〇3*〇-8MgO · I3AI2O3 0.340 0.597 100 7.4 Comparative Example 6 (Ce〇.67, Tb0.33)2〇3 · 2MgO · IIAI2O3 0.340 0.594 102 6.2 Comparison Example 7 (Ce〇.67&gt;Tb〇.33) 2〇3 * 2MgO * I3AI2O3 0.338 0.596 101 4.8 Real drag 38 (Ce〇.67, Tb〇, 33) 2〇3 · l-4 (Mg〇. 93 · Nfa〇.〇7)〇·IIAI2O3 0.245 0.680 .105 5.6 Example 39 (Ce〇.67, Tb〇.33) 2〇3 · 1.4(Mg).93 · Mn〇〇7)0 · 13Al2〇 3 0.243 0.683 107 5.3 Comparative Example 8 (Ce〇.67, Tb〇33) 2〇3 · 2 (Mg〇.95 · Μη〇·〇5)0 · IIAI2O3 0.247 0.675 96 6.0 Comparative Example 9 (Cea67, Tb〇 -33)2〇3 · 2(Mg〇.95 · Μη〇·〇5)0 · 13Al2〇3 0.252 0.673 97 4.2 Example 70 (Ce〇.67, Tb〇.33) 2〇3 _ 0_4MgO · I3AI2O3 0.340 0.567 79 6.7 ❷ Further, based on the results of Table 3 (Examples 30 to 37, 7〇 and Comparative Examples 6, 7), regarding the η value (the total number of moles of Ce+Tb relative to the amount of A1203) ) U. 〇 (X symbol), and 13. 〇 (· symbol) phosphor 'About y value 41 098124986 201011092 ((Ce + Tb) total molar relative amount) Changes in emission luminance of each phosphor accompanied with the variation shown in FIG. Further, although not shown, in the phosphor of the present invention, in the case where the n value is a value other than 11.0 or 13.0, the correlation between the y value and the light emission luminance is also confirmed, which is approximately as shown in FIG. The correlation is a similar relationship. Fig. 7 is a chart showing the luminescence spectrum of each of the phosphors of Examples 3A to 34 and Comparative Example 6 when excited by ultraviolet rays having a wavelength of 254 nm, and Fig. 8 shows the vicinity of the main peak of the spectrum of Fig. 7; The wavelength region spectrum is magnified. In Fig. 7 and Fig. 8, the luminescence spectrum of the phosphor of the embodiment is such that the luminescence intensity at 545 nm is increased with respect to the luminescence intensity at 542 nm, and the luminescence intensity of the minor peaks at 490 nm, 580 nm, and 620 nm is further increased. Since the change is not observed, the relative unnecessary light emission is reduced, and when the phosphor used for the light-emitting display is used, it is predicted to improve the crosstalk. The reason for this is that the secondary peak of 490 nm in the vicinity of 450 nm of blue light emission is not completely filtered by the blue filter, and the color purity of blue is deteriorated. Similarly, the 58 〇 nm luminescence deteriorates the color purity of red. Although the phosphor of the present invention does not change the absolute intensity of these minor peaks, the main luminescence (green 542 nm and &amp; «10) is used to increase the intensity, so that the same effect is obtained when the secondary peaks become lower. . [CAT : Μη phosphor] [Example 38, Example 39, Comparative Example 8, and Comparative Example 9] Seven kinds of raw materials (Ce02, Tb4〇7, MgC03, MnC03, Αΐ2〇3 (α type), _ 〇3, and AIF3) were thoroughly mixed with the compositions shown in Table 3, respectively, 098124986 42 201011092 treated with Examples 30 to 37, 70 and Comparative Example 7, and subjected to calcination, dispersion, washing, drying, and sieving treatment. The Tb2+·Mn2+ of the Examples 38 and 39 and Comparative Examples 8 and 9 were obtained to jointly activate the aluminate phosphor. In addition, the composition was confirmed by ICP. The luminescent color (chromaticity) and relative brightness of the obtained phosphor and the average particle diameter measured by the FSSS method (Fisher Subsieve Sizer method) are shown in Table 3 ° ❺ About chromaticity, relative brightness, and particle size The measurement methods were the same as those of Examples 30 to 37 and 70 and Comparative Examples 6 and 7. Fig. 9 is a chart showing the luminescence spectra of the phosphors of Example 38, Example 39, Comparative Example 8, and Comparative Example 9 excited by ultraviolet rays having a wavelength of 254 nm. As is known from Fig. 9, the phosphors of the examples (38 and 39) are the same as in the case of the CAT phosphor, and it is understood that the luminescence intensity of Μ at a wavelength of 542 nm with respect to 545 nm and Μ near 517 nm is also improve. Further, as shown in Fig. 10, the aluminate phosphor of the present invention (Examples 38 and 39) was relatively absorbed by the luminescence of the substance with respect to the stoichiometric composition (Comparative Examples 8 and 9). improve. As can be seen from Fig. 10, the aluminate phosphor of the present invention having a stoichiometric composition (y = 2.0) shifted in the direction of decreasing y, compared to the stoichiometric composition of the prior phosphor, is contained in VUV having a wavelength of 172 nm. The wavelength region and the wavelength region of the mercury ray having a wavelength of 254 nm are all increased in excitation intensity. In particular, 098124986 43 201011092 is preferably from 140 nm to 300 nm, and more preferably from 180 nm to 300 nm, in the rise of the excitation intensity. (Example according to the third embodiment of the present invention) [Fluorescent body] [Examples 40 to 55, 71, 72 and Comparative Examples 12, 14, and 15] Six kinds of raw materials (ce〇2, Tb407, MgC03, Α12〇3 (α type), Η3Β〇3, and A1F3) are thoroughly mixed in the composition shown in Table 4, filled into 坩埚, and then placed on the phosphor material, covered and contained in water vapor. In a nitrogen atmosphere, the maximum temperature is 1550. (: calcination is carried out for 24 hours in the temperature rise and fall time. η3Β03 and A1F3 in the raw material are fluxes generally used for the production of phosphors. In addition, the values of the columns 1-x, X, y, and n in Table 4, The values of ι_χ, χ, y, and ^ in the above general formula (Cei-xTbx) 203 · yMgO · ηΑ1203 (the ζ is omitted because Μ Μ is omitted), and the values of the Mg shed are Mg in the glory body. Next, the smoldering powder was dispersed, washed, dried, and sieved to obtain Tb-activated acid sulfates of Examples 40 to 55, 71, and 72 and Comparative Examples 12, 14, and 15. In addition, the composition was confirmed by Icp. Examples 40 to 55, 7 and 72, and Comparative Examples 12, 14, and 15 show that the relationship between the 1/10 afterglow time and the relative brightness when the amount of Tb was changed was Main purpose. 098124986 44 201011092 [Table 4]

❹ 评估 The luminescent color (chromaticity), the 1/1 〇 afterglow time, and the average particle diameter of each of the obtained phosphors were evaluated by the following evaluation methods. The results are shown in Table 4. Further, the average particle diameter was measured only for the phosphors of Examples 4 to 50. (a) Chroma: Measured using a color luminance meter (trade name "K200" manufactured by Konica Minolta Co., Ltd.). (b) Relative Brightness: As a standard, the phosphoric acid treatment of the cold-cathode fluorescent lamps and the commercially available cold-phosphorus fluorescent lamps are commercially available as a standard, and the product name is LP-G2 manufactured by Optonix. The luminous intensity of the light is expressed as a relative value at 100 hours. 098124986 45 201011092 (c) Average particle size: Measured according to the FSSS method (Fisher Subsieve Sizer method). (d) l/l 〇 afterglow time: Measured by the spectrophotometer type (phosphorescence short-life) by the F-4500 spectrofluorometer, manufactured by 曰立制. Thereafter, after the irradiation of the ultraviolet ray was stopped, the time (ms) at which the luminescence intensity at the peak wavelength near 54 〇 nm at the start of the measurement was attenuated to 1/10 was obtained. The results of Table 4 (Examples 40 to 55, 71, 72 and Comparative Example 12, Η, 15) are the reference 'fluorescents with a y value of 1 3, an η value of 13. 〇, and a phosphor having a y value of 2,0 and an n value of 13.0, The change of the 1/1 〇 afterglow time of each phosphor associated with the change of the 1-x value (the amount of Ce relative to the amount of Tb) is shown in Fig. η. 'And the respective phosphors accompanying the change in the X value. The change in luminance is shown in Fig. 12. Comparative Example 14 is a stoichiometric composition and the true composition of the known document, + Tb = 2. Further, although not shown, in the phosphor of the present invention, the y value is 13, η In the case where the value is a value other than 13.0, the correlation between the X value and the afterglow time is confirmed to be approximately related to and similar to that shown in Fig. 11. On the other hand, As shown in Fig. 11, when the y value is 2.0 and the η value is 13.0, if the stoichiometric composition is maintained and the amount of yttrium and ytterbium is changed, the shortening effect of the 1/1() afterglow time is relatively changed. On the other hand, as shown in Fig. 12, the lower the value, the higher the brightness tends to be, but the correlation between the brightness and X does not depend on the y value of 098124986 46 201011092. It can be seen that the brightness rapidly decreases when the value is 0.85 or more. [Examples 56 to 61, 80 and Comparative Examples 16 to 19] In the same manner as in the above Example 40, the phosphors of Examples 56 to 61, 80 and Comparative Examples 16 to 19 were produced at the composition ratios shown in Table 5. The results are also combined with the results of the above Example 47, which are shown in Table 5 and Figures 13 and 14 (for the values in Table 5, • the same as Table 4). Here, the X value is fixed to the recommended composition of x = 0.67, so that y In addition, regarding the average particle diameter, only the phosphors of Examples 56 to 61 and 80 and the ratio of φ to Examples 18 and 19 were measured. From the data of the 1/10 afterglow time of Fig. 13, it can be judged that if y is smaller than When y=2 of the stoichiometric composition, the 1/10 afterglow time is rapidly shortened. On the other hand, if it is from the viewpoint of brightness, as shown in Fig. 14, y 0.6 or more is preferable. [Table 5] 1-x X y η Color coordinate brightness residual light Ce Tb Mg A1 X y Y 1/10 afterglow FSSS particle size comparison example 16 0.67 0.33 3.00 6.00 13.0 0.338 0.581 80 6.62 - Comparative Example 17 0.67 0.33 2.00 4.00 13.0 0.341 0.595 101 6.46 - Comparative Example 18 0.67 0.33 1.50 3.00 13.0 0.339 0.597 104 6.55 4.2 Comparative Example 19 0.67 0.33 1.00 2.00 11.0 0.340 0.594 102 6.67 6.2 Example 56 0.67 0.33 0.90 1.80 13.0 0.338 0.596 102 6.38 4.7 Implementation Example 57 0.67 0.33 0.75 1.50 13.0 0.338 0.6 105 6.15 4.7 Example 47 0.67 0.33 0.65 1.30 13.0 0.337 0.602 106 5.76 5.3 Example 58 0.67 0.33 0.60 1.20 13.0 0.338 0.603 106 5.68 5.8 Example 59 0.67 0.33 0.55 1.10 13.0 0.34 0.603 105 5.74 4.6 Example 60 0.67 0.33 0.50 1.00 13.0 0.34 0.597 100 5.09 6.3 Example 61 0.67 0.33 0.40 0.80 13.0 0.34 0.597 89 5.19 7.4 Example 80 0.67 0.33 0.20 0.40 13.0 0.34 0.567 79 4.67 6.7

[Examples 62 to 65, and Comparative Example 20] In the same manner as in the above Example 40, the phosphors of Examples 47 098124986 201011092 62 to 65 and Comparative Example 20 were produced at the composition ratios shown in Table 6. The results are shown in Table 6 and Figure 15, and Figure 16 (the values in Table 6 are the same as Table 4). Here, the X value is fixed to the recommended composition of l-x = 0.33, and the y value is 1.3, so that the value of η is changed. It can be judged from the data of the residual light time of 1/1 of Fig. 15, and if η is less than 7, the 1/10 afterglow time is rapidly increased. On the other hand, η is preferably 11 or more in terms of brightness. [Table 6] 1-x X y η color coordinate brightness residual light Ce Tb Mg A1 X y Y 1/10 residual light FSSS particle size comparison example 20 0.67 0.33 0.65 1.30 6.5 0.331 0.563 63 7.14 4.6 Example 62 0.67 0.33 0.65 1.30 9.0 0.340 0.575 86 5.01 4.4 Example 63 0.67 0.33 0.65 1.30 11.0 0.340 0.598 102 5.27 3.4 Example 64 0.67 0.33 0.65 1.30 20.0 0.339 0.598 98 5.29 3.3 Example 65 0.67 0.33 0.65 1.30 30.0 0.338 0.599 94 5.23 3.0 [White Fluorescent Lamp] [Example 66] The phosphor described in Example 45 was used as a green phosphor, and was converted into a blue phosphor "LP-B4" (ΒΑΜ phosphor) manufactured by Optonix Co., Ltd., and a red color manufactured by Optonix Co., Ltd. Phosphor "LP-RE1" (YOX phosphor) was mixed to produce a white cold cathode lamp with a chromaticity point of (x/y = 0.270/0.240). [Comparative Example 22] A white cold cathode lamp having a chromaticity point of (x/y = 270.270/0.240) was produced as in the above Example 66, except that the phosphor described in Comparative Example 6 was used as the green phosphor. . [Comparative Example 23] 098124986 48 201011092 In addition to the use of green fluorescent body rLP_G2" (LAp phosphor) manufactured by Optonix Co., Ltd. as a green phosphor, the same chromaticity point as in the above Example 66 was made (x/y =白色.270/0.240) white cold cathode lamp. When the lamp brightness of Example 66, Comparative Example 22, and Comparative Example 23 was measured, when the brightness of the lamp of Comparative Example 23 was regarded as 1 ,, the lamps of Comparative Example 22 and Example 66 were all 99. . From this result, it was judged that among the lamp brightness, the aluminate phosphor of the short afterglow time of the present invention has the same brightness as the previous product, and is practical. (Industrial Applicability) The aluminate phosphor of the present invention exhibits higher luminance green luminescence than the previously known Mn-activated yttrium-magnesium aluminate phosphor, and is comparable to the prior product. The near-ultraviolet region has a high luminescence intensity in the visible light region, and the absorption of the ray is also excellent. Further, the aluminate phosphor of the present invention exhibits a synergistic effect with a previously known Tb-doped magnesium-aluminate phosphor and Tb.Mn. Magnesium. High-brightness green light of equal or higher. Further, the aluminate phosphor of the present invention has approximately the same brightness as the conventionally known di-anthracene: living (tetra) magnesium-salt phosphor, and exhibits green luminescence and greatly reduces the afterglow time. The aluminate phosphor of the present invention having the above characteristics is a cold cathode fluorescent lamp, a rare gas lamp, a backlight device, a liquid crystal display device, and a plasma which are excited by a vacuum violet region and an ultraviolet region. It can be used in a wide range of fields such as monitors and coffee makers 098124986 49 201011092. In addition, Japanese Patent Application No. 2008-190855, filed on July 24, 2008, and Japanese Patent Application No. 2008-270155, filed on Jan. 2, 2008, and Japanese Patent Application No. 2009, filed on March 13, 2009 The specification, the scope of the patent application, the drawings and the abstract of the specification of the specification of the specification of BRIEF DESCRIPTION OF THE DRAWINGS (A) in Fig. 1 is an aluminate fluorescent lamp shown by a general formula (CexTbi x) 2 〇 3 · y (Mgi zMnz) 〇 η Α 12 〇 3 (but x = 1) The correlation between the y in the general formula and the illuminating intensity (♦) of the luminescent wavelength of 518 nm and the luminescent intensity (▲) of the luminescent wavelength of 350 nm when excited by ultraviolet light having a wavelength of 254 η π. (B) is a correlation diagram showing the ratio of the above y, the emission intensity of the emission wavelength of 518 nm to the emission intensity of the emission wavelength of 350 nm. 2 is a graph showing the general formula (CexTUWs · yCMgi.zMnJO · ηΑ1203 (but x=l), which is not in the general formula of the phosphor of the acid salt, and the excitation intensity of l72 nm with respect to the excitation intensity of 254 nm. Figure 3 is a graph showing the y and brightness in the general formula of the aluminate phosphor shown by the general formula (〇βχΤνχ)2〇3 · yCMguzMnJO · ηΑ12〇3 (but x=l) Fig. 4 is a graph showing the correlation between n and luminance in a general formula (CexTbkhOs · WMgiJVtnJO · ηΑ12〇3 (but x = 1)) in an aluminate phosphor. 098124986 50 201011092 Fig. 5 is a graph showing the average particle diameter of η and FSSS method (Fisher Subsieve Sizer method) in the aluminate phosphor represented by the general formula (CexTUaC^ · yCMgrzMnJO · ηΑ12〇3 (but x=l) Fig. 6 is a correlation diagram showing the correlation between y and luminance in the aluminate phosphor represented by the general formula (CexTbrxhC^ · yCMghzMnJO · ηΑ1203 • (but z=0), and the correlation between n and luminance. Fig. 7 is a luminescence spectrum of each of the phosphors of Examples 30 to 34 and Comparative Example 6. Fig. 8 is an enlarged view of the main peak of the graph shown in Fig. 7. Fig. 9 is a graph showing the respective luminescence spectra of the phosphors of Examples 38 and 39 and Comparative Examples 8 and 9. Fig. 10 is a view showing the respective excitation spectra of the phosphors of Examples 38 and 39 and Comparative Examples 8 and 9. Fig. 11 is a correlation diagram showing the X and 1/10 afterglow time in the general formula of the fluorate phosphor represented by the general formula (CexTUaC^ · · ηΑ12〇3 10 (but ζ = 0). Fig. 12 is a graph showing the correlation between enthalpy and brightness in the general formula of the aluminate phosphor shown by the general formula (CexTbi_x) 2 〇 3 · yCMghzMnJO · η Α 1203 . (but z = 0). To show the correlation between y and 1/10 afterglow time in the general formula in the aluminate phosphor shown by the general formula (CexTbbxhC^ · yCMgi.JVtnJO · 11AI2O3 (but z = 0). 098124986 51 201011092 Fig. 14 is a graph showing the correlation between y and luminance in the general formula in the aluminate phosphor represented by the general formula (CexTbuxhO yiMgi-zMnJO · η Α 1203 (but z = 0). Correlation diagram between η and 1/10 afterglow time in the general formula in the aluminate phosphor represented by the formula (CexTbbxhC^ · yiMgrzMnJO · ηΑ1203 (but z=0). Fig. 16 is a graph showing the correlation between η and luminance in the general formula of the aluminate phosphor represented by the general formula (CexTbbxhOs · yiMgkMnJO · ηΑ1203 (but ζ = 0). 098124986 52

Claims (1)

201011092 VII. Patent application scope: 1. An aluminate phosphor characterized by the general formula: ^CexTbi-x)2〇3 * y(Mgi.zMnz)0 · ηΑ1203 (However, in the formula, When X, y, z &amp;n is 〇&lt;χ&lt;1, it is a number satisfying the conditions of 1.8, 7$η, respectively, and when χ=i, it satisfies 〇.2Sy$1.8, O.lszy, 7^η The number of conditions). An aluminate phosphor according to the first aspect of the patent application, wherein, in the above general formula, X = 1, 〇.3$d 2 . 3. The aluminate phosphor of claim 2, wherein in the above general formula, X = 1, 0.7 each yg 2 . 4', for example, in the second or third term of the patent patent, the acid salt phosphor, wherein, in the above general formula, a kind of acid crystal phosphor, which is at least 钸 (Ce), 猛 (Μη ), magnesium (g) ^S (Al) and oxygen (〇) is characterized by a ratio of the luminous intensity of the wavelength-independent wavelength to the luminous intensity of the 518 proof of less than 15%. 6. For example, if the patent application is to provide a fixed amount of the aluminate phosphor of the fifth item, wherein the above-mentioned phosphor is expressed by the general formula ~1% τνχ)2〇3 · ^^MgbzMnJO · nAl2〇3' In the formula, X, ν y, z, and η are the numbers satisfying the conditions of x=i, 〇.2SyS1.8, 〇·_1, and 7′, respectively. a phosphor, wherein, in the above general formula, X is 〇 &lt; XC1 y is 0.8^y$1·6. 098124986 53 201011092 8. Aluminate phosphor according to claim 7 of the patent application, wherein In the general formula, X is 0.5$χ$〇.9. 9. The aluminate phosphor according to any one of claims 1 to 3, wherein, in the above general formula, n is 11$η. 10. The aluminate phosphor of any one of claims 7 to 9 wherein 'in the above general formula, z is z = 〇. 11. Aluminate fluorite as claimed in the scope of claim The light body, wherein, in the above general formula, 0.68 Sxg 0.95, z = 0. 12. The aluminate phosphor of claim u, wherein, in the above general formula, 0.7 Sx $ 〇.85. 13' an aluminate a phosphor which is a phosphor composed of at least cerium (Ce), strontium (Tb), magnesium (Mg), indium (A1), and oxygen (〇), and is characterized by &quot;I. The afterglow time is 6.4ms or less. 14. The strontium silicate phosphor of any one of claims 1 to 13 wherein the surface is coated by a coating material. 15. As claimed in claim 14 An aluminate phosphor, wherein the coating material is a carbonate of a rare earth metal. 16. The aluminate phosphor of claim 15 wherein the amount of the rare earth metal carbonate is relatively The phosphor is 〇.〇5~5 wt%. 17_- A method for producing aluminate phosphor, characterized in that the stoichiometric composition of ce, Tb, Mg, Μη and A1 is in the scope of patent application丄 to 098124986 54 201011092 'The ratio of any of items 4 and 6 to the item - Ce compound, several compounds, Mg compound, Mn compound, and AJ compound are mixed and calcined. 18. - Production of salt-reducing phosphor The method is characterized in that the stoichiometric composition formula of ~butb Mg, Mn, and A1 is based on the scope of the patent application. The ratio of any of items 4 to 6 to 12, which can be obtained by heating a Ce compound which becomes an oxide of a sieve (Ce), a Tb 4 composition which can be converted into an oxide of crystallization by heating, can be borrowed The ton compound which is heated to become an oxide of magnesium (Mg), ruthenium can be mixed and calcined by a compound which is heated to become a ruthenium oxide, and an A1 compound which can be converted into an oxide of the ingot (10) by heating. A-type fluorescent lamp characterized by using an aluminate phosphor according to any one of the claims. 20. The fluorescent lamp of claim 19, wherein the glory lamp is a cold cathode fluorescent lamp. The cherries-type cold cathode glory lamp is characterized by any of the patent scopes ^ to -6 - Item _ Salt phosphor is a green phosphor, and a phosphor having a residual time of L 〇 mS or less is used as a blue phosphor, and U is a residual phosphor of 3. Gms or less as a red 鸯22. A cold cathode fluorescent lamp according to claim 21, wherein the blue phosphor is a EU reduction _ 灰石$光体 or 31 活活颔·镇绍酸In the case of salt sputum, the above-mentioned red phosphor is an oxygen-emitting partial phosphor or Eu-activated strontium sulphate. 098124986 55 201011092 23. A backlight unit characterized by using the patent of the 19th or 20th patent A light lamp, or a cold cathode fluorescent lamp of claim 21 or 22. 24. A liquid crystal display device characterized in that the backlight unit of claim 23 is used to make it pseudo-pulsed. 098124986 56