JP6190265B2 - Method for producing barium nitride particles and phosphor - Google Patents
Method for producing barium nitride particles and phosphor Download PDFInfo
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- JP6190265B2 JP6190265B2 JP2013262154A JP2013262154A JP6190265B2 JP 6190265 B2 JP6190265 B2 JP 6190265B2 JP 2013262154 A JP2013262154 A JP 2013262154A JP 2013262154 A JP2013262154 A JP 2013262154A JP 6190265 B2 JP6190265 B2 JP 6190265B2
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- 239000002245 particle Substances 0.000 title claims description 70
- 229910052788 barium Inorganic materials 0.000 title claims description 60
- -1 barium nitride Chemical class 0.000 title claims description 60
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000010298 pulverizing process Methods 0.000 claims description 26
- 230000002269 spontaneous effect Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000001186 cumulative effect Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 7
- 150000004767 nitrides Chemical class 0.000 description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 210000002445 nipple Anatomy 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ZGLFRTJDWWKIAK-UHFFFAOYSA-M [2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]-triphenylphosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC(=O)OC(C)(C)C)C1=CC=CC=C1 ZGLFRTJDWWKIAK-UHFFFAOYSA-M 0.000 description 1
- JENCOQNWECEFQI-UHFFFAOYSA-N azanide;barium(2+) Chemical compound [NH2-].[NH2-].[Ba+2] JENCOQNWECEFQI-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
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Description
本発明は、蛍光体の原料として有用な窒化バリウム粒子の製造法及び該窒化バリウム粒子を用いた蛍光体の製造方法に関する。 The present invention relates to a method for producing barium nitride particles useful as a raw material of a phosphor and a method for producing a phosphor using the barium nitride particles.
窒化バリウムは、白色ＬＥＤ用窒化物蛍光体の原料として広く用いられている。具体的には、Ｂａ2Ｓｉ5Ｎ8：Ｅｕ2+に代表されるようなバリウムを含む窒化物蛍光体やＭＡｌＳｉＮ3：Ｅｕ2+、Ｍ2Ｓｉ5Ｎ8：Ｅｕ2+、ＭＡｌＳｉ4Ｎ7：Ｅｕ2+、Ｍ2Ｓｉ7Ａｌ3ＯＮ13：Ｅｕ2+（式中、Ｍはアルカリ土類元素を示す）などのアルカリ土類元素を一部置換する窒化物蛍光体や酸窒化物蛍光体などが挙げられる。 Barium nitride is widely used as a raw material for nitride phosphors for white LEDs. Specifically, a nitride phosphor containing barium represented by Ba 2 Si 5 N 8 : Eu 2+ , MAlSiN 3 : Eu 2+ , M 2 Si 5 N 8 : Eu 2+ , MAlSi 4 N 7 : Eu 2+ , M 2 Si 7 Al 3 ON 13 : Nitride phosphor and oxynitride partially replacing alkaline earth elements such as Eu 2+ (wherein M represents an alkaline earth element) Examples thereof include phosphors.
窒化バリウムは、金属バリウムを窒素気流中で加熱する方法、バリウムアミドを熱分解する方法、バリウムを水素化し、次いで窒素気流中で加熱する方法等により製造される（特許文献１）、かかる方法において、窒化バリウムは、通常１００ｍｍ程度であり１０ｍｍ以上の塊として得られる。このような塊状では蛍光体原料としては使用できないため、合成された窒化バリウムはマイクロメートルオーダーの粒子に粉砕される。 Barium nitride is produced by a method in which metal barium is heated in a nitrogen stream, a method in which barium amide is thermally decomposed, a method in which barium is hydrogenated and then heated in a nitrogen stream (Patent Document 1). The barium nitride is usually about 100 mm and is obtained as a lump of 10 mm or more. Since such a lump cannot be used as a phosphor material, the synthesized barium nitride is pulverized into micrometer order particles.
しかしながら、粒子状の窒化バリウムは、窒化カルシウムや窒化ストロンチウムなどに比べて大気中の水分や酸素と反応しやすく、自然発火性を示しやすい。従って、運搬中の容器の破損などにより、大気中の水分や酸素と反応し、火災に繋がる可能性がある。
従って、本発明の課題は、自然発火を生じない窒化バリウムの製造法を提供することにある。さらには、窒化バリウム粒子を用いて安全に蛍光体を製造する方法を提供することを課題とする。
However, particulate barium nitride is more likely to react with moisture and oxygen in the atmosphere than calcium nitride, strontium nitride, and the like, and tends to exhibit spontaneous ignition. Therefore, there is a possibility that the container reacts with moisture and oxygen in the atmosphere due to breakage of the container being transported, leading to a fire.
Accordingly, an object of the present invention is to provide a method for producing barium nitride which does not cause spontaneous ignition. It is another object of the present invention to provide a method for producing a phosphor safely using barium nitride particles.
そこで本発明者は、合成した窒化バリウムの粉砕条件及び粒度分布と発火性との関係について検討してきたところ、全く意外にも、粒子径が小さすぎる場合よりも、ある一定の粒度分布の範囲にある窒化バリウム粒子とすることにより自然発火が防止されることを見出し、本発明を完成した。 Therefore, the present inventor has examined the relationship between the pulverization condition and particle size distribution of the synthesized barium nitride and the ignition property, and surprisingly, it has a certain particle size distribution range rather than the case where the particle size is too small. It has been found that spontaneous combustion is prevented by using certain barium nitride particles, and the present invention has been completed.
すなわち、本発明は、次の〔１〕〜〔３〕を提供するものである。 That is, the present invention provides the following [1] to [3].
〔１〕粒子径１０ｍｍ以上の窒化バリウムを、露点−１００℃〜−５０℃、酸素濃度０．１ｐｐｍ〜１０００ｐｐｍの不活性ガス雰囲気中で粉砕し、最大粒径が１０ｍｍ未満、平均粒子径１５μｍ以上であり、体積基準の累積値で１０μｍ以下が４０％未満、２０μｍ以下が７０％以下、３０μｍ以下が９０％以下の粒度分布を有する粒子とすることを特徴とする自然発火を示さない窒化バリウム粒子の製造法。
〔２〕露点−１００℃〜−５０℃、酸素濃度０．１ｐｐｍ〜１０００ｐｐｍの不活性ガス雰囲気中で粉砕して得られる、最大粒径が１０ｍｍ未満、平均粒子径１５μｍ以上であり、体積基準の累積値で１０μｍ以下が４０％未満、２０μｍ以下が７０％以下、３０μｍ以下が９０％以下の粒度分布を有する自然発火を示さない窒化バリウム粒子。
〔３〕〔２〕に記載の窒化バリウム粒子を平均粒子径１０μｍ以下に粉砕し、該粉砕物を用いて蛍光体原料に調合した後焼成するか、あるいは〔２〕に記載の窒化バリウム粒子を用いて蛍光体原料を調合し、平均粒子径１０μｍ以下に混合粉砕した後焼成することを特徴とする蛍光体の製造方法。
[1] Barium nitride having a particle size of 10 mm or more is pulverized in an inert gas atmosphere having a dew point of −100 ° C. to −50 ° C. and an oxygen concentration of 0.1 ppm to 1000 ppm, the maximum particle size is less than 10 mm, and the average particle size is 15 μm or more. Barium nitride particles that do not exhibit spontaneous ignition, characterized by having a particle size distribution with a volume-based cumulative value of 10 μm or less of less than 40%, 20 μm or less of 70% or less, and 30 μm or less of 90% or less Manufacturing method.
[2] Dew point −100 ° C. to −50 ° C., obtained by pulverization in an inert gas atmosphere having an oxygen concentration of 0.1 ppm to 1000 ppm, the maximum particle size is less than 10 mm, the average particle size is 15 μm or more, Barium nitride particles which have a particle size distribution in which the cumulative value is less than 40% at 10 μm or less, 70% or less at 20 μm or less, and 90% or less at 30 μm or less and does not show spontaneous ignition.
[3] The barium nitride particles as described in [2] are pulverized to an average particle size of 10 μm or less, and prepared by using the pulverized product as a phosphor raw material, followed by firing, or the barium nitride particles as described in [2] A method for producing a phosphor, comprising preparing a phosphor raw material using the mixture, mixing and pulverizing the phosphor to an average particle size of 10 μm or less, and firing the mixture.
本発明により得られる窒化バリウム粒子は、自然発火を生じないので、安全に流通させることができる。さらには、安全に高品質の蛍光体を製造することができる。 Since the barium nitride particles obtained by the present invention do not cause spontaneous ignition, they can be safely distributed. Furthermore, a high-quality phosphor can be manufactured safely.
本発明の窒化バリウム粒子の製造法について説明する。 The manufacturing method of the barium nitride particle | grains of this invention is demonstrated.
原料となる窒化バリウムは、既知の方法により製造される粗粒子又は塊であればよい。このような窒化バリウムの製造法としては、前記特許文献１に記載の方法等が挙げられる。原料窒化バリウムの粒子径は１０ｍｍ以上であり、１５〜５０ｍｍ程度が好ましい。ここで、原料窒化バリウムの純度は、９９％以上、さらに９９．９％以上であるのが、蛍光体としての利用性の点から好ましい。また、高純度の窒化バリウムでなければ発火の問題も生じない。ここで、純度はＸ線回折で決定できる。 The barium nitride used as a raw material may be coarse particles or lumps produced by a known method. Examples of such a method for producing barium nitride include the method described in Patent Document 1. The particle diameter of the raw material barium nitride is 10 mm or more, preferably about 15 to 50 mm. Here, the purity of the raw material barium nitride is preferably 99% or more, and more preferably 99.9% or more, from the viewpoint of availability as a phosphor. Moreover, the problem of ignition does not occur unless the barium nitride is of high purity. Here, the purity can be determined by X-ray diffraction.
窒化バリウム粗粒子又は塊は、露点−１００℃〜−５０℃、酸素濃度０．１ｐｐｍから１０００ｐｐｍの不活性ガス雰囲気中で粉砕する。露点が−５０℃より高い条件又は酸素濃度が１０００ｐｐｍより高い条件で粉砕を行うと、粉砕過程で発火を生じるおそれがある。このような条件とするには、乾燥したＮ2、Ａｒ、Ｈｅ等の不活性ガス雰囲気とすればよい。より好ましい条件は、露点−７０℃〜−９０℃、酸素濃度０．５〜１００ｐｐｍのＮ2、Ａｒ又はＨｅガス雰囲気である。 Barium nitride coarse particles or lumps are pulverized in an inert gas atmosphere having a dew point of −100 ° C. to −50 ° C. and an oxygen concentration of 0.1 ppm to 1000 ppm. If pulverization is performed under conditions where the dew point is higher than −50 ° C. or the oxygen concentration is higher than 1000 ppm, ignition may occur during the pulverization process. In order to achieve such conditions, a dry inert gas atmosphere such as N 2 , Ar, or He may be used. More preferable conditions are an N 2 , Ar or He gas atmosphere having a dew point of −70 ° C. to −90 ° C. and an oxygen concentration of 0.5 to 100 ppm.
粉砕手段としては、遊星ボールミル粉砕、乳針による粉砕、ＳＵＳ製ポットを用いたポットミル粉砕等が挙げられる。このうち、粉砕効率や忌避成分の混入不安など点から、遊星ボールミル粉砕、乳針による粉砕が好ましい。 Examples of the pulverizing means include planetary ball mill pulverization, pulverization with a nipple, and pot mill pulverization using a SUS pot. Of these, planetary ball mill pulverization and pulverization with a nipple are preferred from the standpoint of pulverization efficiency and fear of mixing repellent components.
粉砕後の窒化バリウム粒子は、必要によりふるい分けし、１０ｍｍのふるい目を全通するようにする。得られる窒化バリウムの最大粒子径は、蛍光体原料としての輸送や調合、粉砕時の取扱い性、蛍光体中の組成が均一となり蛍光体の品質が低下しないよう他の原料との混合性の点から、１０ｍｍ未満以下であり、８ｍｍ以下が好ましく、３ｍｍ以下がより好ましく、１ｍｍ以下がさらに好ましい。また、窒化バリウムの平均粒子径は１５μｍ以上であり、好ましくは２０〜５０００μｍ、より好ましくは３０〜２０００μｍである。 The barium nitride particles after pulverization are screened as necessary so that the 10-mm screen is completely passed through. The maximum particle size of the obtained barium nitride is the transportability and blending as a phosphor raw material, the handling property at the time of pulverization, and the miscibility with other raw materials so that the composition in the phosphor becomes uniform and the quality of the phosphor does not deteriorate. To less than 10 mm, preferably 8 mm or less, more preferably 3 mm or less, and even more preferably 1 mm or less. Moreover, the average particle diameter of barium nitride is 15 micrometers or more, Preferably it is 20-5000 micrometers, More preferably, it is 30-2000 micrometers.
窒化バリウム粒子の粒度分布は、３０μｍ以下の小さい粒子が少ないことが好ましく、体積基準の累積値で１０μｍ以下が４０％未満、２０μｍ以下が７０％以下、３０μｍ以下が９０％以下である。この粒度分布よりも細かい場合には、発火性を示すため好ましくない。より好ましい粒度分布は、体積基準の累積値で１０μｍ以下が２０％未満、２０μｍ以下が４５％以下、３０μｍ以下が７０％以下である。 The particle size distribution of the barium nitride particles is preferably such that there are few small particles of 30 μm or less, 10 μm or less is less than 40%, 20 μm or less is 70% or less, and 30 μm or less is 90% or less by volume-based cumulative value. If it is finer than this particle size distribution, it is not preferable because it shows ignition properties. More preferable particle size distribution is a cumulative value based on volume of 10 μm or less of less than 20%, 20 μm or less of 45% or less, and 30 μm or less of 70% or less.
本発明によって得られた窒化バリウム粒子は、大気中において、自然発火を示さない。従って、種々の形態の窒化物蛍光体原料として取扱いやすいものである。 The barium nitride particles obtained by the present invention do not show spontaneous ignition in the atmosphere. Therefore, it is easy to handle as various forms of nitride phosphor raw materials.
本発明の窒化バリウム粒子を用いて、蛍光体を製造する方法としては、本発明の窒化バリウム粒子と窒化ストロンチウム、窒化カルシウム、窒化珪素、窒化アルミニウム等の所要の他の窒化金属と、ユーロピウム、セリウム等の賦活剤元素を含む化合物が調合された粉体を焼成して、蛍光体を得る方法が挙げられる。詳細には（１）本発明の窒化バリウム粒子を平均粒子径１０μｍ以下に粉砕し、該粉砕物を用いて蛍光体原料に調合した後、焼成するか、あるいは（２）本発明の窒化バリウム粒子を用いて蛍光体原料を調整し、平均粒子径１０μｍ以下に混合粉砕した後焼成する方法が挙げられる。より具体的には、（１）窒化バリウム粒子を輸送及び／又は保管し、次いで、露点−１００℃〜−５０℃、酸素濃度０．１ｐｐｍから１０００ｐｐｍの不活性ガス雰囲気中で平均粒子径１０μｍ以下に粉砕し、その他原料と混合した調合原料を焼成しても良いし、（２）窒化バリウム粒子を輸送及び／又は保管した後、次いで、露点−１００℃〜−５０℃、酸素濃度０．１ｐｐｍから１０００ｐｐｍの不活性ガス雰囲気中で該窒化バリウム粒子とその他所要の原料を平均粒子径１０μｍ以下に混合粉砕した調合原料を焼成しても良い。 As a method for producing a phosphor using the barium nitride particles of the present invention, the barium nitride particles of the present invention and other required metal nitrides such as strontium nitride, calcium nitride, silicon nitride, aluminum nitride, europium, cerium, etc. Examples include a method of firing a powder prepared with a compound containing an activator element such as to obtain a phosphor. Specifically, (1) the barium nitride particles of the present invention are pulverized to an average particle size of 10 μm or less, and the pulverized material is used to prepare a phosphor material, followed by firing, or (2) the barium nitride particles of the present invention. The phosphor raw material is adjusted using, and the mixture is pulverized to an average particle size of 10 μm or less and then fired. More specifically, (1) The barium nitride particles are transported and / or stored, and then the average particle diameter is 10 μm or less in an inert gas atmosphere having a dew point of −100 ° C. to −50 ° C. and an oxygen concentration of 0.1 ppm to 1000 ppm. The mixed raw material may be pulverized and mixed with other raw materials, or (2) after the barium nitride particles are transported and / or stored, the dew point is −100 ° C. to −50 ° C., and the oxygen concentration is 0.1 ppm. To 1,000 ppm in an inert gas atmosphere, the prepared raw material obtained by mixing and grinding the barium nitride particles and other required raw materials to an average particle size of 10 μm or less may be fired.
前記（１）の方法の粉砕された窒化バリウム粒子、あるいは前記（２）の方法の粉砕された調合原料の粒度は、蛍光体中の組成が均一となり蛍光体の品質が低下しないよう平均粒径１０μｍ以下、好ましくは５μｍ以下とする。該調合原料は、通常なら発火する微粒子の窒化バリウムを含むが、他の原料と混合されているので発火することはなく、安全に焼成工程に移行できる。 The particle size of the pulverized barium nitride particles obtained by the method (1) or the pulverized preparation raw material obtained by the method (2) is such that the composition in the phosphor is uniform and the quality of the phosphor is not deteriorated. 10 μm or less, preferably 5 μm or less. The blended raw material usually contains fine particles of barium nitride that ignite, but since it is mixed with other raw materials, it does not ignite and can be safely transferred to the firing step.
前記（１）の方法は、窒化バリウム粒子を粉砕した後に他の原料と混合するまでの取り扱い時に発火や酸化の恐れがあるので、常に発火する恐れがない前記（２）の方法を用いることが好ましい。 In the method (1), there is a risk of ignition or oxidation during handling until the barium nitride particles are pulverized and then mixed with other raw materials. preferable.
粉砕手段としては、遊星ボールミル粉砕、乳針による粉砕、ＳＵＳ製ポットを用いたポットミル粉砕等が挙げられる。このうち、粉砕効率や忌避成分の混入不安など点から、遊星ボールミル粉砕、乳針による粉砕が好ましい。 Examples of the pulverizing means include planetary ball mill pulverization, pulverization with a nipple, and pot mill pulverization using a SUS pot. Of these, planetary ball mill pulverization and pulverization with a nipple are preferred from the standpoint of pulverization efficiency and fear of mixing repellent components.
蛍光体調合原料の組成は、Ｂａ2Ｓｉ5Ｎ8：Ｅｕ2+に代表されるようなバリウムを含む窒化物蛍光体やＭＡｌＳｉＮ3：Ｅｕ2+、Ｍ2Ｓｉ5Ｎ8：Ｅｕ2+、ＭＡｌＳｉ4Ｎ7：Ｅｕ2+、Ｍ2Ｓｉ7Ａｌ3ＯＮ13：Ｅｕ2+（式中、Ｍはアルカリ土類元素を示す）となるように窒化金属と賦活剤元素を調合すればよい。 The composition of the phosphor blending raw material is a nitride phosphor containing barium represented by Ba 2 Si 5 N 8 : Eu 2+ , MAlSiN 3 : Eu 2+ , M 2 Si 5 N 8 : Eu 2+ , MAlSi 4 N 7: Eu 2+, M 2 Si 7 Al 3 ON 13: Eu 2+ ( wherein, M represents an alkaline-earth element) may be formulated activator element and a metal nitride such that.
蛍光体調合原料は、１２００℃以上２２００℃以下で焼成することにより蛍光体を製造することができる。焼成は、窒素を含有する不活性雰囲気で行い、窒素ガス単独、窒素とアルゴン又は水素との混合ガス、アンモニアガスを用いることができる。また、ガスの圧力は特に制限はないが、常圧で行うのが経済的で好ましい。 The phosphor blending raw material can produce a phosphor by firing at 1200 ° C. or more and 2200 ° C. or less. Firing is performed in an inert atmosphere containing nitrogen, and nitrogen gas alone, a mixed gas of nitrogen and argon or hydrogen, or ammonia gas can be used. The gas pressure is not particularly limited, but it is economical and preferable to carry out at normal pressure.
次に実施例を挙げて本発明をさらに詳細に説明する。 EXAMPLES Next, an Example is given and this invention is demonstrated still in detail.
参考例１
グローブボックスにて耐圧容器中に金属バリウムを４００ｇ仕込み、水素圧力を０．９ＭＰａ、保持温度１００℃、保持時間１２時間の条件下で水素化バリウムを合成した。次に、管状炉（長さ１０００ｍｍ，内径８０ｍｍ）にて窒素フロー下保持温度９００℃、保持時間１２時間の条件において窒化バリウムを得た。得られた窒化バリウムの塊の粒径は長さ１００ｍｍ、太さ５０ｍｍ程度であった。得られた窒化バリウムの純度は、ＸＲＤにより９９％以上であることを確認した（図１）。
Reference example 1
400 g of metal barium was charged in a pressure vessel in a glove box, and barium hydride was synthesized under the conditions of a hydrogen pressure of 0.9 MPa, a holding temperature of 100 ° C., and a holding time of 12 hours. Next, barium nitride was obtained in a tubular furnace (length 1000 mm, inner diameter 80 mm) under conditions of a holding temperature of 900 ° C. under a nitrogen flow and a holding time of 12 hours. The particle diameter of the obtained barium nitride lump was about 100 mm in length and about 50 mm in thickness. The purity of the obtained barium nitride was confirmed to be 99% or more by XRD (FIG. 1).
実施例
参考例１で得られた窒化バリウムを露点−７０〜−９０℃、酸素濃度０．５ｐｐｍ〜１００ｐｐｍに保たれたグローブボックスにて遊星ミル容器（窒化ケイ素製５００ｍｌ）に仕込み、遊星ボールミルによる粉砕または乳鉢による粉砕（手粉砕）および分級（７５μｍ）を行い、窒化バリウム粒子を得た。粉砕・分級条件は表１に示す通りである。
Example Barium nitride obtained in Reference Example 1 was charged into a planetary mill container (500 ml made of silicon nitride) in a glove box maintained at a dew point of −70 to −90 ° C. and an oxygen concentration of 0.5 ppm to 100 ppm. Pulverization or pulverization with a mortar (hand pulverization) and classification (75 μm) were performed to obtain barium nitride particles. The pulverization / classification conditions are as shown in Table 1.
各サンプルの粒度分布及び自然発火が生じるか否かを試験した結果を、（表２）及び（表３）に示す。
粒度分布は、レーザー回折・散乱法を用いた日機装（株）製マイクロトラックＨＲＡにて測定した。自然発火が生じるか否かは、国連勧告可燃性物質類自然発火性物質判定試験により判定した。具体的には、１〜２ｍＬの粉状物質を約１ｍの高さから不燃材の表面に注ぎ、落下中又は落下後５分以内に物質が発火するかどうかを観察した。肯定的な結果が得られるまで、この手順を６回行った。
Table 2 and Table 3 show the particle size distribution of each sample and the results of testing whether spontaneous ignition occurs.
The particle size distribution was measured with a Nikkiso Co., Ltd. Microtrac HRA using a laser diffraction / scattering method. Whether or not spontaneous ignition occurs was determined by the UN-Recommended Combustible Substances Pyrophoric Substance Determination Test. Specifically, 1-2 mL of powdery substance was poured onto the surface of the non-combustible material from a height of about 1 m, and it was observed whether the substance ignited during the fall or within 5 minutes after the fall. This procedure was repeated 6 times until a positive result was obtained.
（表１）〜（表３）より、蛍光体製造時に必要とされる平均粒径１０μｍ以下に調整した場合は、発火することがわかる。一方、本発明の方法により得られた特定の粒子径及び粒度分布を有する窒化バリウム粒子は、自然発火を生じないことがわかる。 From (Table 1) to (Table 3), it can be seen that when the average particle size is adjusted to 10 μm or less, which is required at the time of manufacturing the phosphor, ignition occurs. On the other hand, it turns out that the barium nitride particle | grains which have the specific particle diameter and particle size distribution obtained by the method of this invention do not produce spontaneous combustion.
実施例７
比較的多くの窒化バリウムを用いる蛍光体組成であるＢａ2Ｓｉ5Ｎ8の比になるように、露点−７０〜−９０℃、酸素濃度０．１ｐｐｍから１００ｐｐｍの不活性ガス雰囲気中で、比較例１で得られた窒化バリウム粉体と窒化ケイ素粉末を混合し、自然発火性試験を行ったところ、自然発火性は認められなかった。
したがって、蛍光体の調合原料とした場合には、通常なら発火する微粒子の窒化バリウムを含んでいても自然発火を生じないことがわかる。
Example 7
Comparison was made in an inert gas atmosphere having a dew point of −70 to −90 ° C. and an oxygen concentration of 0.1 ppm to 100 ppm so that the ratio of Ba 2 Si 5 N 8 , which is a phosphor composition using a relatively large amount of barium nitride. When the barium nitride powder and silicon nitride powder obtained in Example 1 were mixed and subjected to a spontaneous ignition test, no spontaneous ignition was observed.
Therefore, it can be seen that when the phosphor is prepared as a raw material, spontaneous ignition does not occur even if fine particles of barium nitride that normally ignite are included.
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