WO2006052008A1

WO2006052008A1 - Silicate fluorescent material powder and process for producing the same

Info

Publication number: WO2006052008A1
Application number: PCT/JP2005/021069
Authority: WO
Inventors: Keiji Ono; Toshinori Isobe; Hiroshi Inukai; Kensaku Horie
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2004-11-12
Filing date: 2005-11-10
Publication date: 2006-05-18
Also published as: JP2006137851A; TW200626499A

Abstract

This invention provides a high-luminance silicate fluorescent material powder and a process for producing the same. The silicate fluorescent material powder comprises at least one element, selected from the group consisting of Mg and Zn, and Si and satisfies formula (1). R ≤ 8 (1) wherein R represents b/a × 100 where a and b are determined by steps (i) to (iv): (i) for a blank test, the average value (x) and the standard deviation σ of signal strength for each of Mg, Zn and Si are measured without placing any silicate fluorescent material in a measuring cell in an analyzer; (ii) a silicate fluorescent material powder is placed in a measuring cell in the analyzer to measure signal strength for each of Mg, Zn and Si of particles contained in the powder; (iii) the number a of particles in which the signal strength of at least one element selected from the group consisting of Mg and Zn is not less than x + 3σ, is measured; and (iv) in the above (iii), the number b of particles in which the signal strength of Si is less than x + 3σ, is measured.

Description

Kay Lanlan powder and its difficult method

The present invention relates to gay acid and its $ ¾i method.

Light

Background leakage.

«The body is a vacuum winning line excitation such as PDP ¾ ¾ ?, a three-wavelength type hard lamp is ultraviolet such as a backlight for display«) It is used for the excitation by light of the light, and for the generation of electricity such as a cathode ray tube.

For example, a silicate is known as a ^ 6 body difficulty excited by a vacuum winning line (Japanese Patent Laid-Open No. 2000-302).

In addition, as a ^^ method of the silica ^^ powder, a method is known in which two or more metal compounds are mixed using a pole mill, and the resulting gold compound mixture is obtained (JP-A-2). 0 0 4— 1 6 1 9 8 1).

Kay Hikari (This powder did not have sufficient brightness. Disclosure of the Invention

An object of the present invention is to share a key powder having high brightness and a method thereof.

As a result of studying the gay mil ^ body powder exhibiting high luminance, the present inventors have come true with the present invention. The present invention removes the gaiic acid: ^^ body powder that contains at least one selected from the group consisting of Mg and Zn and Si and satisfies the formula (1).

R≤8 (1),

[R is (b / a) X I 0 0, and a and b are determined in steps (i) to (iv). (0 As a blank test, measure the average value x, MP mo of each signal bow of Mg, z n and s i before putting the powder in the measuring cell of the analyzer.

(ii) Putting the powder in the measuring cell of the separator and measuring the Mg, Zn and Si f-number bow ^ J of the particles contained in the powder;

(iii) At least one ί 言号艘艘 selected from the group consisting of Mg and Zn is x +

3 Count the number of particles a that are greater than or equal to σ,

(iv) Of hate (i i i), measure the number of borns «b in which the signal bow daughter of S i is less than x + 3 σ. ]

In addition, the present invention iifts an element including a selfish client's body powder.

Furthermore, the present invention relates to a method for producing a tm½ body comprising steps (1) and (2).

(1) A metal compound mixture that is converted into six carboxylic acids by baking is ground by a belly crusher to obtain a mixture,

(2) Have a mixture. : Forms for inventing

Kay Enomoto Powder

The body powder of the present invention contains at least one selected from the group consisting of Mg and Zn and Si, and preferably contains Eu and: n as an activator for the compound represented by the formula (2). Includes at least one selected.

mM ² 〇ηη2 S i 0 ₂ (2) In formula (2), M ¹ is at least one selected from the group consisting of Mg and Zn, and M ² is at least one selected from the group consisting of C a, S r and B a.

In the formula (2), m is 0.5 or more and 3.5 or less, preferably 1.5 or less, and n is 0.5 or more, 2.5 or less, preferably 1.5 or less. In the case of the phosphor powder, R is 8 or less, preferably 6 or less, more preferably 5 or less. The lower limit of R is 0.

R is the value of at least one signal bow selected from Mg and Zn when measuring the signal bow of Mg, Zn and Si for particles contained in the m ^ m ^ body powder. Calculated by the following equation from the number b of particles CO in which at least one signal 選ば selected from Mg and Z n is equal to or greater than a certain value and the signal arch i of S i is a certain value: To do.

(b / a) X 1 0 0

In detail, a and b are obtained by the method of steps (i) to (iv). Step (i) is a blank t test, and before inserting the gay body into the measurement cell of the branch tree, measure the average values x, m and Mg, Zn and Si of the respective signal bow. The

In step (ii), the Mg, Zn and S i signals for individual particles of the caustic acid ^^ powder

Measure ¾ 艘. At step (m), the average value x obtained at step ω,

Based on o and the data obtained in step (ii), the number of particles a in which at least one signal selected from the group consisting of Mg and Zn is x + 3σ or more is measured. In step (O), the number b of particles of S i (iii) whose S i signal key is less than x + 3σ is measured. Examples of the separation device include Zo, ° -ticle analyzer (manufactured by Horiba, Ltd., DP-1100). The number of particles to be measured is usually 100 or more, preferably 200 or more. The key body is excited by irradiation of light in the region from vacuum rays, ultraviolet rays, and rays to blue (blue), and emits high-luminance light. In addition, the caisic acid: ^ 体 body is excited by X-rays, X-rays, and electrical irradiation, and emits bright light. 1?

The ^^ of the present invention includes a selfish key body powder. m -u, usually kay Including phosphor powder in addition to comfort.魏 »For example, vacuum ultraviolet excitation such as PDP gas lamp ^ ¹ 6», ultraviolet excitation such as three-wavelength fluorescent lamp and backlight for liquid crystal display ^ 6¾? A white light emitting diode, preferably vacuum ultraviolet light excitation. The eaves emit high-intensity light and are useful as various displays and lighting devices.

The PDP usually includes a back substrate, a phosphor layer, a transparent substrate, an m body layer, and a surface substrate. For example, the PDP can be made difficult by the method described in Japanese Patent Application Laid-Open No. 10-195 428, and the I ^ method includes, for example, steps (a) to (d) At least one of the blue phosphor, the red body, and the green body in (a) is a selfish silica powder.

(a) a step of obtaining a phosphor paste by mixing a blue body, a red phosphor, and a rod, respectively, with a noinda (for example, a cellulose compound, polyvinyl alcohol) and sickle medium;

(b) Blue phosphor paste, red ^ fflm ^ paste, and green phosphor paste on the inner surface of the back substrate and the stripe-shaped substrate surface with the address dragon and the partition wall surface. Apply each (by screen printing etc.), approx. 300 ° C ~ approx. 60

A process of forming an m½ body layer within a range of 0,

(c) a step of superimposing a surface glass substrate provided with a transparent electrode and a bath comforter in the direction directly on the obtained phosphor layer and provided with an if¾ layer and a protective layer on the inner surface; (d) A process of forming a space by enclosing ffi rare gases (X e, N e, etc.) through the interior surrounded by the back substrate and the front glass substrate.

Further, the rare gas lamp may be S ^ by the same operation as the above method except that the above-mentioned gaiic acid ^ "6 powder is used as a raw material. — 2 5 6 9 The method M can be achieved by the method described in the gazette, for example, including the steps (e) to (0) and the blue m½ body, red body, and green body in step (e). At least one of these is a hateful body powder.

(e) a step of preparing a body paste by dispersing a blue phosphor, a red body and a body in a solvent (polyethylene oxide aqueous solution),

(f) A process of applying a phosphor paste to the inner surface of the glass bulb and applying grass.

(^ The glass bulb 4 0 0~9 0 0 ° C Debe and one king, the glass bulb inner surface ^ ¹ body layer in the form ^ ^ "Ru step,

(h) a step of sealing β stem of glass norb,

(i) The process of forming a discharge space after glazing inside a glass norb and then containing rare gas (A r, K r, N e, etc.) and mercury, sealing the exhaust tube, and attaching a cap.

In addition, the backlight for the display may be subjected to the same operation as in the above method using the above-mentioned key powder as a raw material. For example, the white diode can be obtained by the method described in Japanese Patent Application Laid-Open Nos. 11-3 1 8 4 5 and 2 0 2 2 2 8 8 4 6 and can emit light in a blue region. Seal the semi-luminous light emitting element with a transparent resin such as epoxy resin, and place the above-mentioned key powder so as to cover the surface. A combination of the above phosphor powders of the phosphor powder may be used. Gay body way

The method for producing a key body powder of the present invention includes a step (1) of obtaining a mixture by grinding a metal compound mixture with a powder.

The metal compound mixture can be any material that can be made into 6 bodies with integrity. For example, the following gold compound may be mixed and prepared. The metal compound is, for example, a compound of silicon, magnesium, m-manganese, and europium. These oxides, oxides, m-oxides, rhogenides, sulfur oxides, etc. can be oxidized at high temperatures. Usually, in addition to selfishness, barium, strontium, calcium, germanium, aluminum, ruthenium, scandium, yttrium, lanthanum, gadolinium, cerium, prasedium, neodymium, samarium, terbium, dysprosium, holmium, Compound of erylebium, thorium, ytterbium, nium, bismuth, and oxides of these oxides or hydroxides, & m,, rhogenide, lanthanum, and sulfur, etc. It is done. Mixing may be performed using, for example, a pole mill, a V-type mixer, or m. Mixing may be performed by either table testing or wet processing, but the mixed raw material does not cause dissolution and the like: ^ is wet power. In order to satisfy the molar ratio of the metal elements (caine, magnesium, manganese, europium, nojum, strontium, calcium, etc.) contained in the key m ^ m ^ powder, It can be prepared by weighing and mixing, Ca sr Eu MgS i ₂ _{6 6}ケイケイ ½ ½ ½, calcium, strontium carbonate, europium oxide, refractory magnesium, silicon dioxide, Ca: S What is necessary is just to prepare a metal compound mixture by weighing and mixing so that the molar ratio of r: Mg: Eu: Si is 0.892: 0.100: 0.0.008: 1: 2. In addition, to ®i the Kei body represented by Ca ^ Sr ^ Eu ^ MgS i 2 〇 _6:! ^, Calcium Carbonate, Strontium Pit, Palladium Oxide, Key Magnesium, Silicon Dioxide, C: Sr: Mg: Eu: Si molar ratio is 0.49: 0.49: 1: 0 02: 2 Weigh and mix to prepare a gold compound mixture.

Ba ^ S r ₁₅ Eu _{a (B} MgS i ₂ 0 ₈ represents the age of the silicon ^ m¾ body, »Barium, strontium carbonate, Palladium oxide, magnesium, silicon dioxide, Ba: S A metal compound mixture may be prepared by weighing and mixing so that the molar ratio of r: Mg: Eu: Si CD is 0.48: 2.5: 1: 0.02: 2.

The mixture mixture may contain a flux, and the flux only needs to be in good faith and enhance the crystallinity of the casing. Examples of fluxes include boron oxide and ammonium chloride. In addition, the flux may be added after being reduced to α of the metal compound before mixing, energizing the metal compound mixture, or pulverizing the gold compound mixture. mn mm, equipped with a container, a buffer in the container, and a winning part (eg, wing, pin, disk) to win the prize, eg, Arai Yuichi, Pearl Mill, Bead Mill, Agate Wet This is a wet split of thighs and heels. As a flour material ^ powder, Daino Mill (trade name, Shinmaru Enterprises company $ 1), Avex Mill (trade name, Kotobuki m ^^ ± m, Super Avex Millire (trade name, Kotobuki Shikikai ¾¾), OB Miffre (trade name, Yuichi Boe ^^;

For example, the container, freshness, and separation part are ceramic (eg, zirconia, alumina, silicon nitride, silicon carbide), metal, glass, resin, preferably ceramic, shelf More preferably, it is zirconia. It is preferable that 嫩! 嫩 is 0.03 mm or more and 4 mm or less. , Grinding should be performed using powder mash, with the peripheral speed of the wing, pin, or disk being lm / sec or more.

Powder flour is usually wet. It can be done by mixing the metal compound mixture and solvent (for example, water) to obtain a slurry before introducing it into the powder. The slurry may be prepared by adding components from the viewpoint of improving the dispersibility of the metal compound mixture. Examples of organic conversion include organic carboxyls such as sodium carboxylates (polyacrylic sodium, etc.), ammonium carboxylates (ammonium polyacrylates, etc.); ethylamine, trimethylamine, tri Examples include amines such as ethanolamine. Min TO has a low metal content, and is preferably an ammonium polycarboxylate.

The powder is usually obtained by mixing a gold compound mixture and a solvent (for example, water) and putting the resulting slurry through the slurry inlet of the powder. The slurry is discharged from the m w slurry outlet. The discharged slurry may be returned to the crusher from the slurry inlet and viewed. The number of circulations is usually 1 to 10 times. Usually, the resulting slurry is thighed to obtain a mixture. The koji may be performed by a method in which the slurry is directly dried, or a method in which the rally is solid-separated by central separation and the obtained solid is dried. Vehicle disgust is usually 20 ° C. or higher, preferably 90 ° C. or higher, and usually 30 ° C. or lower, preferably 20 ° C. or lower. For example, the direct transfer may be performed by, for example, carrying, evaporation, or spray dryer. In addition, the mixture obtained from the thigh may be crushed or sieved. Keying process of the phosphor powder, and further, the process of grinding the mixture obtained in step (1)

Includes (2).

If the mixture obtained in step a) contains a metal hydroxide, carbon m, halide, sulfur or the like that decomposes at high temperatures to become an oxide, the previous mixture may be calcined. «May be performed at 5500 ° C or higher and 950 or lower, and may be performed in any of a reactive gas atmosphere, an oxidizing atmosphere such as a large atmosphere, and a reactive atmosphere. Further, the mixture obtained by fibering may be pulverized. «Is usually the highest iifig is 1 0 0 0. C or more, 1400 ° C or less, 10 ° 0 ° C or more, 1400 ° or less time to be passed 0.5 hours or more and 50 hours or less . Makoto, cranes, argon-like gas atmospheres; air, soot, M ^ nitrogen, ^^-oxygen atmospheres like argon; hydrogen containing 0.1 to 10% of hydrogen It may be carried out in a sex atmosphere such as water-containing argon containing 0.1 to 10% by weight of a crane or τκ element, preferably in an atmosphere. Dredging may be performed more than once. The key ^ powder method preferably includes the step (3) of pulverizing the product obtained in the step (2). In addition to the step (3), the step of obtaining the product obtained in the step (3) ( More preferably, 4) is included. The pulverization may be performed using, for example, a pole mill or a jet mill under the same conditions as in step (4) in step (4). In the absurd method, it is more preferable to repeat step (3) and step (4) in ¾S from the viewpoint of improving the luminance of the gay phosphor powder. In the case of leaving the phosphor powder, the product may be washed or spread, and the product or powder thereof may be washed. Cleaning may be performed using, for example, water or acid. According to the hate method, a high-luminance silica powder is selected, which includes, for example, at least one selected from the group consisting of Mg and Zn and Si, and satisfies the formula (1). An acid salt powder is obtained. Male example The present invention will be described in more detail with reference to difficult examples, but the present invention is not limited to these examples. Reference example

[Slurry tone S8

The container was filled with water (trade name “SN Dispa Isanto 5468”, San Nopco 0.5 wt. Of water. Then, the calcium-free product name “Super High ^^ Calcium CS · 3N-A”, CaC〇 ₃ , Ube material M), flame strontium (trade name "high-Document雕strontium SW-K", SrC0 _3, Sakai chemical Engineering ^ $ £>, oxidation Yu opening Piumu (Eu ₂ 〇 _3, Shinsha匕,, base ' «Magnesium (trade name" High Magnesium ", MgO content: 42.0%, Kyowa Chemical Leakage, silicon dioxide (trade name" AEROS IL2 00 ", Si 0 ₂ , made by Nippon Aerosil), Ca: Weigh so that the molar ratio of Sr: Eu: Mg: Si is 0.8892: 0.0.100: 0.0.008: 1: 2, and stir them in a container for 20 minutes. Thus, a slurry having a solid content of 12% by weight was obtained.

Picture

Slurry 1. 24 kg was processed using a pole mill (capacity: 5 L) under the following conditions.

Separation: Zirconia beads with a diameter of 5 mm, 10 kg

Time: 4 hours

Times ^: 60 r pm

After the treatment, the slurry was pulverized, pulverized and fined at 120 ° C for 20 hours to obtain a powder of 300 m or less mm

Was discussed at 900 ° C under the atmosphere and crushed. The resulting powder 2 basket% H ₂ containing chromatic N ₂ atmosphere, and «2 hours at 1180 ° C, and Kona碎, the Ca S r Eu MgS i represented by ₂ 〇 ₆ ^ ¹ _έ powder _REF Obtained. [The so-called powder

Enomoto emitted blue light under a vacuum line lt with an excimer 1 46 nm lamp ("H0012", Ushi: ^ «,) in a vacuum chamber of 6.7 Pa (5X10" ² Torr) or less. Job # ¾) * The brightness of _REF is set to 100. The brightness of the phosphor powder obtained in the following difficult examples is expressed as the relative value of the brightness of phosphor » _REF .

In addition, R was obtained for 3687 particles in phosphor powder _REF using a particle analyzer ("DP-1000", HORIBA, Ltd.). For Mg, the channel of the detector detector was set to 1, and the wavelength 285. Spectral at 210 nm was measured at high pressure ® at a magnification of 1. 00. For Si, the detector channel of the instrument was set to 2 and the spectral at wavelength 288.16 Onm was measured at high pressure. Measured at a magnification of 1.00 R was 8. 81 Cat Example 1

[Slurry preparation SS

The container was filled with water (trade name “SN Dispa Isanto 5468”, San Nopco 0.5% by weight water. Next, calcium carbonate (trade name “Ultra High Concealment Calcium CS · 3N-A”, CaC 〇 _3, ^^ Materials), flame strontium (brand name "high-fiber纖strontium SW-K", SrC0 _3, Sakai Gakuegi, oxidation Yu opening Piumu (Eu ₂ 〇 _3, Shinkama匕, thigh of碰magnesium (trade name "Kokagiomomuki magnesium", M G_〇 content: 42.0%, manufactured by Kyowa chemical Engineering纖, silicon dioxide (trade name "AEROS IL2 00", S I_〇 _2, made in Japan Aerojiru), Ca: Weigh so that the molar ratio of Sr: Eu: Mg: Si is 0.8892: 0.0.100: 0.0.008: 1: 2 and add them to the weave while stirring. A slurry with a solid content of 12 dragon% was obtained. 55.7 kg of the slurry was treated under the following conditions using a Dyno mill (trade name “Dyno mill MULTI LAB type”, capacity: 1.46 L, Shinmaru Enterprises IS).

Slurry yarn: 450 g / min,

Disk peripheral speed: 4.5m / sec

External request: Yes'

Number of Si in slurry: 2 times

Xiemoto: Zirconia beads with a diameter of 1 mm, 4.5 kg.

After the treatment, the slurry was crushed at 120 ° C. for 20 hours, pulverized, and crushed IJ to obtain a mixture of 300 m3 or less.

[Makoto

The mixture was carefully pulverized at 900 ° C in a large atmosphere. The resulting powder 2 # ¾% Eta ₂ containing New ₂ atmosphere for 2 hours舰at 1180 ° C, and Kona碎, represented by _{_{_{Ca 0M S r 0. Ia)}}} Eu a008 Mg S i 2 〇 ₆ Obtained Ranmoto powder 1.

[Fine powder powder

麵本powder 1, 6. ^{7 P a (5 X 10- 2} T orr) following the vacuum chamber, excimer 14 6 nm lamp ( "H0012", © sheet; manufactured by ¾,) vacuum ^^ by SenTeru JTF It was blue. The luminance of phosphor powder 1 was 106. Further, R was obtained for 215 9 particles contained in the housing powder 1 using a particle analyzer. R was 6.95. Difficult example 2

In male example 1, phosphor band 2 was obtained by performing the same operation, repeating the bandit and subsequent powder cake twice. The body powder 2 had a luminance of 132. Also 1 ^ body R was determined for a particle 2 6 2 3 contained in powder 2 using a particle analyzer. R was 5.87. Difficult example 3

In Example 1, phosphor powder 3 was obtained by performing the same operation 1 ^, repeating ぉ and subsequent powdering 3 times. Body powder 3 has a luminance of 14. Met. In addition, R was obtained using a particle analyzer for 2 6 6 9 particles contained in the approximate powder 3. R was 4.50. Male Example 4

The body powder 3 was mixed with 0,3N soot for 3 hours, filtered, and dried at 120 ° C. to obtain phosphor powder 4. The body powder 4 had a luminance of 1 4 5. R was obtained using a particle analyzer for 2 4 7 particles contained in body powder 4. R was 3.03. Availability of production

According to the present invention, a phosphor powder exhibiting high luminance is desired. Since the key body powder exhibits high brightness in vacuum, it is suitable for vacuum knitting such as PDP gas lamps. Further, according to the present invention, a method for producing a high-luminance silica powder is described.

Claims

The scope of the claims

1. A key body powder containing at least one selected from the group consisting of Mg and Zn and S i and satisfying the formula (1).

R≤8 (1)

[R is (bZa) X I 0 0, and a and b are determined in steps (i) to (iv).

(i) As a blank test, measure the average value x and M m σ of each signal bow of Mg, z n and s i before putting the caustic powder into the measuring cell of the device.

(ii) Minutes! Put the silica powder in the measurement cell and measure the signal strength of Mg, Zn and Si of the particles contained in the powder.

(iii) measuring the number of particles a in which at least one signal bow selected from the group consisting of Mg and Zn is x + 3σ or more,

(iv) Of hate (iii), measure the number b of particles whose signal of S i is less than x + 3 mm. ]

2. The silicate phosphor according to claim 1, wherein the silicate powder comprises at least one selected from the group consisting of Eu and Mn as a neutralizing agent and a compound represented by Powder.

mM ² 0 ηΜΌ 2 S i 0 ₂

[M ¹ is at least one selected from the group consisting of Mg and Zn, M ² is at least one selected from the group consisting of C a, S r and B a, and m is 0.5 or more 3 .5 or less

n is 0.5 or more and 2.5 or less. ]

3. Including the silica powder according to claim 1 or 2 ¾¾¾? .

4. The eaves are selected from the vacuum ultraviolet light, eaves and white diodes. Claim 3 tm ^

5. A method for dripping the key body powder including the steps (1) and (2).

(1) Use «to obtain a mixture of the metal なる composite compound that becomes the body of the silica 匕 by ί» »» 枠枠枠枠枠、

(2) Be confused.

6. The method according to claim 5, wherein the silica body comprises a compound represented by ^; and at least one selected from the group consisting of Eu and Μη as a tongue.

mM ² 0 nM ^L 0 2 Si 0 ₂

It is 0.5 or more and 2.5 or less. ]

7. The method according to claim 5 or 6, further comprising step (3).

(3) Powdering the product obtained in step (2).

8. The method of claim 7, further comprising step (4).

(4) What should be obtained in step (3).

9. Use as a powder of silica that satisfies at least one selected from the group consisting of Mg and Zn and Si (1).

R≤8 (1)

[R is (bZa) X I 0 0, and a and b are obtained in steps (i) to (iv). (i) As a blank test, measure the average value x, mm ^ o of each signal bow of Mg, z n and s i before putting the key substance into the measuring cell of the instrument.

(ii) Put the caustic powder in the measuring cell of the minute! ^ and measure the Mg, Zn and Si signal bows of the particles contained in the powder.

(iii) At least one signal bow selected from the group consisting of Mg and Zn is x + Measuring the number of particles a that are greater than or equal to 3σ,

(iv) The number of particles b in which the signal bow girl of S i is less than x + 3 times out of (iii). ]