JP4315371B2 - Infrared-visible conversion phosphor - Google Patents
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- JP4315371B2 JP4315371B2 JP2003319132A JP2003319132A JP4315371B2 JP 4315371 B2 JP4315371 B2 JP 4315371B2 JP 2003319132 A JP2003319132 A JP 2003319132A JP 2003319132 A JP2003319132 A JP 2003319132A JP 4315371 B2 JP4315371 B2 JP 4315371B2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 46
- 238000006243 chemical reaction Methods 0.000 title claims description 18
- 239000002245 particle Substances 0.000 claims description 37
- 238000009826 distribution Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 10
- 229910021538 borax Inorganic materials 0.000 claims description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 8
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 8
- 239000006104 solid solution Substances 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 230000001186 cumulative effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 15
- 229910052796 boron Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 229910052691 Erbium Inorganic materials 0.000 description 5
- 229910052769 Ytterbium Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UAHZTKVCYHJBJQ-UHFFFAOYSA-N [P].S=O Chemical compound [P].S=O UAHZTKVCYHJBJQ-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- -1 rare earth oxysulfide Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- Luminescent Compositions (AREA)
Description
本発明は、赤外線照射により緑色発光する蛍光体に関する。更に詳しくは、適当な赤外線発光源と組み合わせて、高付加価値製品、秘密書類の真偽確認コードないし偽造防止のために使用する蛍光体に関する。また、赤外線検出システムに使用できる蛍光体に関する。 The present invention relates to a phosphor that emits green light by infrared irradiation. More particularly, the present invention relates to a high-value-added product, a genuine document verification code for secret documents, or a phosphor used for preventing counterfeiting in combination with a suitable infrared light source. Moreover, it is related with the fluorescent substance which can be used for an infrared detection system.
赤外線で励起したとき、可視光を発光する赤外可視光変換蛍光体は公知であり、多数の低エネルギーの赤外線フォトン照射により高エネルギーの可視光フォトンを発生させる目的で、Ｙｂ及びＥｒで賦活された蛍光体が知られている。
このような蛍光体としては、たとえば、下記の非特許文献１にはフッ化物を主成分とする蛍光体が記載されている。これらのフッ化物蛍光体の赤外可視光変換効率は高いが、製造工程において、酸素を混入しないように製造することが難しく、湿度・気温等の環境条件の影響を受け易く、品質の安定性の点で問題がある。
これに対して、希土類酸化硫化物蛍光体は変換効率は上記フッ化物蛍光体に比べると若干劣るが、製造が比較的容易で、上述の環境条件のほかに有機溶媒、アルカリなどにも強く、過去にもいくつかの特許提案がなされている。
Infrared-visible light-converting phosphors that emit visible light when excited with infrared light are known and activated with Yb and Er for the purpose of generating high-energy visible light photons by irradiating many low-energy infrared photons. Known phosphors are known.
As such a phosphor, for example, the following Non-Patent Document 1 describes a phosphor mainly composed of fluoride. Although these fluoride phosphors have high infrared-visible light conversion efficiency, they are difficult to manufacture without mixing oxygen in the manufacturing process, are easily affected by environmental conditions such as humidity and temperature, and are stable in quality. There is a problem in terms of.
In contrast, rare earth oxysulfide phosphors are slightly inferior in conversion efficiency to the above-mentioned fluoride phosphors, but are relatively easy to manufacture, and are resistant to organic solvents, alkalis, and the like in addition to the environmental conditions described above. Several patent proposals have been made in the past.
例えば下記特許文献１には（Ｌａ，Ｇｄ，Ｙ）2Ｏ2Ｓ：Ｙｂ，Ｅｒ蛍光体、下記特許文献２には（Ｌａ，Ｇｄ，Ｙ）2Ｏ2Ｓ：Ｙｂ，Ｅｒ，Ｈｏ蛍光体、下記特許文献３には（Ｓｃ，Ｌｕ）2Ｏ2Ｓ：Ｙｂ，Ｅｒ蛍光体、下記特許文献４にはＹ2Ｏ2Ｓ：Ｙｂ，Ｅｒ蛍光体が記載されている。
これらの希土類酸化硫化物蛍光体は、通常希土類酸化物にアルカリ金属炭酸塩と硫黄とを反応させて製造する。加熱すると、アルカリ金属多硫化物が生成し、希土類酸化物を硫化して酸化硫化物を生成する。この焼成物を水洗するとアルカリ金属成分が除去され、所望の酸化硫化物蛍光体が得られる。
For example, the following Patent Document 1 discloses (La, Gd, Y) 2 O 2 S: Yb, Er phosphor, and the following Patent Document 2 describes (La, Gd, Y) 2 O 2 S: Yb, Er, Ho phosphor. Patent Document 3 below describes (Sc, Lu) 2 O 2 S: Yb, Er phosphor, and Patent Document 4 below discloses Y 2 O 2 S: Yb, Er phosphor.
These rare earth oxysulfide phosphors are usually produced by reacting a rare earth oxide with an alkali metal carbonate and sulfur. When heated, an alkali metal polysulfide is produced, and the rare earth oxide is sulfided to produce an oxysulfide. When the fired product is washed with water, the alkali metal component is removed, and a desired oxysulfide phosphor is obtained.
これらの蛍光体は、赤外線を照射することにより緑色に発光することから、この特性を利用したセキュリティシステム、たとえば適当な赤外線発光源と組み合わせて、高付加価値製品としての証明書類、秘密書類、紙幣などにこれらの蛍光体を印刷塗布して、偽造防止等の目的として使用される。このとき、印刷塗布性の観点から、小粒子であり粒子形状が揃っている蛍光体が望まれている。
一般的に赤外可視光変換効率は蛍光体の粒子径に依存して、小粒子になるほど発光輝度は低下する。また、蛍光体を小粒子化するために、焼成後の蛍光体をボールミル等で粉砕して小粒子蛍光体を得る方法や、分級によって小粒子部分を選別して、目的とする粒径を備えた小粒子蛍光体を得る方法が知られている。 しかしながら、この様な方法で得られた蛍光体はボールミル等のストレスによる発光輝度の更なる低下や分級法による歩留まりの低下が起こり、好ましくない。
Since these phosphors emit green light when irradiated with infrared rays, they are combined with a security system using this characteristic, for example, an appropriate infrared emission source, such as certificates, secret documents, banknotes as high-value-added products. These phosphors are used for the purpose of preventing counterfeiting by printing and applying these phosphors. At this time, from the viewpoint of print applicability, a phosphor that is small and has a uniform particle shape is desired.
In general, the infrared-visible light conversion efficiency depends on the particle diameter of the phosphor, and the emission luminance decreases as the particle size decreases. In addition, in order to reduce the size of the phosphor, a method of obtaining a small particle phosphor by pulverizing the phosphor after firing with a ball mill or the like, and selecting a small particle portion by classification to provide a target particle size. A method for obtaining a small particle phosphor is known. However, the phosphor obtained by such a method is not preferable because a further decrease in emission luminance due to stress such as a ball mill or a decrease in yield due to a classification method occurs.
このため、小粒子で高効率の蛍光体の開発が望まれていた。酸化硫化物蛍光体の発光特性向上のために蛍光体の融剤（フラックス）として、例えば下記非特許文献２にはヒ酸塩、ゲルマン酸塩、リン酸塩及び硫酸塩を用いることが好ましいと記載されている。このほかに上述の特許文献４にはアルカリ金属フッ化物のＫＦを使用することが記載されている。
しかしながら、これらの工夫によっても光出力は十分とはいえず、更なる改良が期待されていた。
However, even with these devices, the light output is not sufficient, and further improvements have been expected.
本発明の目的は、上記に説明した従来技術に鑑み、小粒子で赤外変換効率の高い希土類酸化硫化物蛍光体を提供することである。
本発明者等は上記目的のために種々合成方法の検討を行った。その結果、該当蛍光体に微量のホウ素（Ｂ）を導入し、これを固溶させることにより、高効率で小粒子な赤外可視変換蛍光体が得られることを見出し、本発明に至ったものである。
An object of the present invention is to provide a rare earth oxysulfide phosphor having small particles and high infrared conversion efficiency in view of the above-described prior art.
The present inventors have studied various synthesis methods for the above purpose. As a result, it was found that by introducing a small amount of boron (B) into the corresponding phosphor and dissolving it , a highly efficient and small-particle infrared-visible conversion phosphor can be obtained, and the present invention has been achieved. It is.
上記の課題に鑑み、本発明のうち第１の発明に係る赤外可視変換蛍光体は、原料混合においてホウ酸ナトリウム（Ｎａ ２ Ｂ ４ Ｏ ７ ）を添加することにより製造される蛍光体であって、一般式が（Ｌｎ１−ｘ−ｙＹｂｘＥｒｙ）２Ｏ２Ｓ（ただし、ＬｎはＹ、Ｇｄ及びＬａから選ばれる少なくとも１種以上の元素であり、ｘは０．０２≦ｘ≦０．２、ｙは０．０２≦ｙ≦０．２）で表される蛍光体に、ホウ素Ｂが０．００１重量％以上、０．５重量％以下の範囲で固溶させ、固溶されていない場合に比べて、粒度分布の巾を狭め、かつ累積粒度分布の中央値であるD５０の値を小さくしたことを特徴とする。
ＬｎはＹ、Ｇｄ、Ｌａから選ばれた少なくとも１種以上の元素を用いることができるが、特にＹを含む蛍光体は化学的安定性が良好で好適である。ここでＹｂの濃度ｘを０．０２≦ｘ≦０．２、Ｅｒの濃度ｙを０．０２≦ｙ≦０．２の範囲に限定した理由は、発光輝度がこれらの濃度に依存し、この範囲外では十分な発光が得られないからである。本発明の赤外可視変換蛍光体のホウ素Ｂ含有量を、固溶した状態で０．００１重量％以上、０．５重量％以下に限定した理由は、０．００１重量以下ではホウ素のない従来の蛍光体と特性が変わらず、０．５重量以上になると蛍光体の粒度は小さくなるが、蛍光体の輝度低下も大きくなり好ましくないからである。
In view of the above problems, the infrared-visible conversion phosphor according to the first invention of the present invention is a phosphor produced by adding sodium borate (Na 2 B 4 O 7 ) in a raw material mixture. Te general formula (Ln 1-x-y Yb x Er y) 2 O 2 S ( however, Ln is at least one or more elements selected from Y, Gd and La, x is 0.02 ≦ x ≦ 0.2, y is 0.02 ≦ y ≦ 0.2) Boron B is dissolved in the range of 0.001 wt% or more and 0.5 wt% or less. Compared to the case where it is not, the width of the particle size distribution is narrowed, and the value of D50, which is the median value of the cumulative particle size distribution, is reduced.
Ln can use at least one element selected from Y, Gd, and La, and a phosphor containing Y is particularly preferable because of good chemical stability. Here, the reason why the Yb concentration x is limited to 0.02 ≦ x ≦ 0.2 and the Er concentration y is limited to the range of 0.02 ≦ y ≦ 0.2 is that the emission luminance depends on these concentrations. This is because sufficient light emission cannot be obtained outside the range. The reason why the boron B content of the infrared-visible conversion phosphor of the present invention is limited to 0.001% by weight or more and 0.5% by weight or less in a solid solution state is 0.001% by weight or less. This is because when the weight is 0.5 weight or more, the particle size of the phosphor is decreased, but the luminance of the phosphor is greatly decreased, which is not preferable.
この蛍光体は小粒子であり粒子形状が揃っているため、適当な赤外線発光源と組み合わせて、高付加価値製品の証明、秘密書類、紙幣などに印刷塗布して、偽造防止等の目的のために使用される際の印刷塗布性の観点から、好適である。
For phosphors This we have all are particle shape small particles, in combination with a suitable infrared light emitting sources, proof of the high value-added products, and print coating secret documents, such as the bill, the purpose of forgery prevention Therefore, it is preferable from the viewpoint of print applicability when used.
ここでホウ素（Ｂ）はホウ酸根の形で蛍光体中に固溶すると考えられ、焼成工程において酸化硫化物蛍光体の結晶同志が融合し、結晶成長を妨げる方向に働くが、発光特性には悪い影響を与えないと推定している。このように発光輝度が低下せずに、しかも粒子径を抑制することがホウ素（Ｂ）を固溶させることの効果であり、これにより従前のような、焼成後の粉砕作業が軽減または不要となり、粉砕ストレスによる輝度低下が抑制されるため、本発明の蛍光体はホウ素を固溶させていない蛍光体に比べて、抑制された粒子径として粒子形状が揃っており、粒度分布の巾を狭めることによって、粒度分布がシャープになり、しかも赤外線励起での発光輝度も向上する。
Here, boron (B) is considered to be a solid solution in the phosphor in the form of boric acid radicals, and the crystals of the oxysulfide phosphor are fused in the firing process, which acts to hinder crystal growth. Estimated not to have a negative effect. In this way, the emission luminance is not lowered and the particle size is suppressed by the effect of dissolving boron (B), thereby reducing or eliminating the pulverization work after firing as before. The phosphor of the present invention has a uniform particle shape with a suppressed particle size and narrows the width of the particle size distribution compared to a phosphor not containing boron as a solid solution , because luminance reduction due to crushing stress is suppressed. As a result, the particle size distribution becomes sharp, and the luminance of light emitted by infrared excitation is also improved.
上記組成としたことにより、抑制された粒子径として蛍光体粒子形状の揃った、シャープな粒度分布を持つ小粒子で高輝度の赤外可視変換蛍光体を得ることができる。
By adopting the above composition, it is possible to obtain a high- intensity infrared-visible conversion phosphor with small particles having a sharp particle size distribution with a uniform particle size as a suppressed particle size .
以下、本発明の実施例につき説明する。
（１）実施例１
酸化イットリウム（Ｙ2Ｏ3）を３８３．９ｇ（１．７モル）に、酸化イッテルビウム（Ｙｂ2Ｏ3）を７８．８ｇ（０．２モル）、酸化エルビウム（Ｅｒ2Ｏ3）を３８．３ｇ（０．１モル）加え、よく混合して希土類酸化物粉末５０１ｇを得た。さらに、硫黄（Ｓ）７５ｇ、ホウ酸ナトリウム（Ｎａ2Ｂ4Ｏ7）３．０ｇ及び炭酸ナトリウム（Ｎａ2ＣＯ3）１００ｇを加えて、よく混合した後、アルミナ容器に入れて、１，１５０℃に保ちながら３時間焼成した。
Examples of the present invention will be described below.
(1) Example 1
383.9 g (1.7 mol) of yttrium oxide (Y 2 O 3 ), 78.8 g (0.2 mol) of ytterbium oxide (Yb 2 O 3 ), and 38. g of erbium oxide (Er 2 O 3 ). 3 g (0.1 mol) was added and mixed well to obtain 501 g of rare earth oxide powder. Further, 75 g of sulfur (S), 3.0 g of sodium borate (Na 2 B 4 O 7 ) and 100 g of sodium carbonate (Na 2 CO 3 ) were added and mixed well. Firing was performed for 3 hours while maintaining the temperature.
室温まで冷却後、５％の硝酸水溶液で洗浄を３回繰り返し、蛍光体粒子の凝集を除去するために、直径２ｍｍのアルミナボール５００ｇと脱イオン水５００ｇを添加して、ミリング処理を行い、更に脱イオン水で５回蛍光洗浄を行った。その後、濾過、乾燥、篩別工程を経て本発明の赤外可視変換蛍光体を得た。この実施例１に係る赤外可視変換蛍光体の化学分析の結果、ホウ素を６００ｐｐｍ含有するものであった。
（２）実施例２
実施例１の原料混合において、ホウ酸ナトリウム（Ｎａ2Ｂ4Ｏ7）を３．０ｇ添加する代わりに、０．１５ｇ添加混合した混合原料を用いて、以下の工程は実施例１と同様にして、本発明に係る赤外可視変換蛍光体の実施例２を試作した。
After cooling to room temperature, washing with a 5% nitric acid aqueous solution is repeated three times, and in order to remove the aggregation of phosphor particles, 500 g of alumina balls having a diameter of 2 mm and 500 g of deionized water are added and milling is performed. Fluorescent washing was performed 5 times with deionized water. Then, the infrared visible conversion phosphor of the present invention was obtained through filtration, drying and sieving steps. As a result of chemical analysis of the infrared-visible conversion phosphor according to Example 1, boron was contained at 600 ppm.
(2) Example 2
In the raw material mixing of Example 1, instead of adding 3.0 g of sodium borate (Na 2 B 4 O 7 ), using the mixed raw material added and mixed with 0.15 g, the following steps were the same as in Example 1. Thus, Example 2 of the infrared-visible conversion phosphor according to the present invention was prototyped.
（３）実施例３
実施例１の原料混合において、ホウ酸ナトリウム（Ｎａ2Ｂ4Ｏ7）を３．０ｇ添加する代わりに、４．５ｇ添加混合した混合原料を用いて、以下の工程は実施例１と同様にして、本発明に係る赤外可視変換蛍光体の実施例３を試作した。
（４）実施例４
実施例１の原料混合において、ホウ酸ナトリウム（Ｎａ2Ｂ4Ｏ7）を３．０ｇ添加する代わりに、６．０ｇ添加混合した混合原料を用いて、以下の工程は実施例１と同様にして、本発明に係る赤外可視変換蛍光体の実施例４を試作した。
(3) Example 3
In the raw material mixing of Example 1, instead of adding 3.0 g of sodium borate (Na 2 B 4 O 7 ), using the mixed raw material added and mixed with 4.5 g, the following steps were the same as in Example 1. Thus, Example 3 of the infrared-visible conversion phosphor according to the present invention was prototyped.
(4) Example 4
In the raw material mixing of Example 1, instead of adding 3.0 g of sodium borate (Na 2 B 4 O 7 ), using the mixed raw material with 6.0 g added and mixed, the following steps were the same as in Example 1. Thus, Example 4 of the infrared-visible conversion phosphor according to the present invention was prototyped.
（５）実施例５
実施例１の原料混合において、ホウ酸ナトリウム（Ｎａ2Ｂ4Ｏ7）を３．０ｇ添加する代わりに、２５．０ｇ添加混合した混合原料を用いて、以下の工程は実施例１と同様にして、本発明に係る赤外可視変換蛍光体の実施例５を試作した。
（６）比較例１
酸化イットリウム（Ｙ2Ｏ3）を３８３．９ｇ（１．７モル）に、酸化イッテルビウム（Ｙｂ2Ｏ3）を７８．８ｇ（０．２モル）、酸化エルビウム（Ｅｒ2Ｏ3）を３８．３ｇ（０．１モル）加え、よく混合して希土類酸化物粉末５０１ｇを得た。さらに、硫黄（Ｓ）７５ｇ、炭酸ナトリウム（Ｎａ2ＣＯ3）１００ｇを加えて、よく混合した後、アルミナ容器に入れて、１，１５０℃に保ちながら３時間焼成した。
(5) Example 5
In the raw material mixing of Example 1, instead of adding 3.0 g of sodium borate (Na 2 B 4 O 7 ), using the mixed raw material added and mixed with 25.0 g, the following steps were the same as in Example 1. Thus, Example 5 of the infrared-visible conversion phosphor according to the present invention was prototyped.
(6) Comparative Example 1
383.9 g (1.7 mol) of yttrium oxide (Y 2 O 3 ), 78.8 g (0.2 mol) of ytterbium oxide (Yb 2 O 3 ), and 38. g of erbium oxide (Er 2 O 3 ). 3 g (0.1 mol) was added and mixed well to obtain 501 g of rare earth oxide powder. Further, 75 g of sulfur (S) and 100 g of sodium carbonate (Na 2 CO 3 ) were added and mixed well, then placed in an alumina container and baked for 3 hours while maintaining at 1,150 ° C.
以下の工程は上記実施例１と同様にして、比較用の蛍光体を試作した。化学分析の結果から、この比較例１に係る蛍光体のホウ素含有量は検出限界（１０ｐｐｍ）未満であった。
（７）比較例２
実施例１の原料混合において、ホウ酸ナトリウム（Ｎａ2Ｂ4Ｏ7）の混合添加量を３５ｇにする以外は、実施例１と同様にして、比較例２の蛍光体を試作した。
（８）測定方法
赤外線励起による発光輝度評価には、赤外線光源（波長９００ｎｍ〜１，０００ｎｍの範囲）を用い、蛍光体の発光輝度はミノルタの輝度計ＬＳ−１００を用いて測定した。
The following steps were carried out in the same manner as in Example 1 above, and a comparative phosphor was prototyped. From the result of the chemical analysis, the boron content of the phosphor according to Comparative Example 1 was less than the detection limit (10 ppm).
(7) Comparative Example 2
A phosphor of Comparative Example 2 was made in the same manner as in Example 1 except that the amount of sodium borate (Na 2 B 4 O 7 ) added was 35 g in the raw material mixing of Example 1.
(8) Measuring method For the evaluation of emission luminance by infrared excitation, an infrared light source (wavelength range of 900 nm to 1,000 nm) was used, and the emission luminance of the phosphor was measured using a Minolta luminance meter LS-100.
また、蛍光体の粒度分布は島津のＳＡＬＤ−２１００レーザー回折粒度測定装置で測定した。
（９）結果
下記の表１に、比較例１を標準（１００）にしたときの発光輝度並びに累積粒度分布において、分布の１０％に相当するＤ１０値、分布の５０％に相当する中央値Ｄ５０値並びに分布の９０％に相当するＤ９０値、そして各試料の化学分析の結果から、試料中に含まれるホウ素（Ｂ）の分析値を示す。
The particle size distribution of the phosphor was measured with a SALD-2100 laser diffraction particle size analyzer from Shimadzu.
(9) Results In Table 1 below, in the light emission luminance and cumulative particle size distribution when Comparative Example 1 is standard (100), the D10 value corresponding to 10% of the distribution and the median value D50 corresponding to 50% of the distribution The analysis value of boron (B) contained in the sample is shown from the value, D90 value corresponding to 90% of the distribution, and the result of chemical analysis of each sample.
この表から分かるように、ホウ素の固溶により、発光輝度は向上するのに対して、粒度分布の中央値であるＤ５０、及びＤ９０は減少し、粒度が小径になると共に、粒度分布がシャープになることが分かる。ホウ素量が更に多くなると、輝度は減少傾向になるので、ホウ素量の好ましい範囲は１０ｐｐｍから５，０００ｐｐｍの範囲である。この範囲内であれば、小粒子で高輝度の赤外可視変換蛍光体が得られる。
また、発明者は、ミリング工程を繰り返し実施し、配合量及びその他は実施例１ないし実施例５と同様な工程により製造されたＤ９０が３．２μｍ、４．７μｍ、３．６μｍ、２．７μｍ及び１．８μｍである本発明に係る赤外可視変換蛍光体を試作した。
As can be seen from this table, the emission luminance is improved by the solid solution of boron, whereas the median values of D50 and D90 of the particle size distribution are decreased, the particle size becomes smaller and the particle size distribution becomes sharper. I understand that Since the luminance tends to decrease as the boron content further increases, the preferred range of the boron content is in the range of 10 ppm to 5,000 ppm. Within this range, an infrared-visible conversion phosphor with small particles and high brightness can be obtained.
In addition, the inventor repeatedly performed the milling process, and the blending amount and other D90 produced by the same processes as in Examples 1 to 5 were 3.2 μm, 4.7 μm, 3.6 μm, 2.7 μm. And an infrared-visible conversion phosphor according to the present invention having a thickness of 1.8 μm.
さらに、比較対象として、ミリング工程を繰り返し実施し、配合量及びその他は比較例１及び比較例２と同様な工程により製造された、Ｄ９０が６．２μｍ及び２．２μｍである蛍光体も試作した。そして上記と同様に発光輝度及びホウ素量を測定し、確認したところ、ホウ素の固溶により、発光輝度は向上するのに対して、粒度を小径にし、かつ粒度分布の巾を狭めることによって、粒度分布がシャープになり、さらに、ホウ素量が多くなると、発光輝度は減少傾向になるので、ホウ素量の好ましい範囲は１０ｐｐｍから５，０００ｐｐｍの範囲であることを確認している。
なお、本発明の上記各実施例及び比較例は例示を目的としたもので、本発明の範囲を制限するものではない。本発明の他の実施例は本発明書の内容の検討から当業者には自明であろう。
Furthermore, as a comparison object, the milling process was repeatedly performed, and the phosphors having D90 of 6.2 μm and 2.2 μm manufactured by the same processes as those of Comparative Example 1 and Comparative Example 2 were also produced. . Then, the emission luminance and the amount of boron were measured and confirmed in the same manner as described above. The emission luminance was improved by the solid solution of boron, whereas the particle size was reduced by reducing the particle size and reducing the width of the particle size distribution. As the distribution becomes sharper and the amount of boron increases, the luminance of light emission tends to decrease. Therefore, it is confirmed that the preferable range of the amount of boron is in the range of 10 ppm to 5,000 ppm.
In addition, each said Example and comparative example of this invention are for the purpose of illustration, and do not restrict | limit the scope of the present invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the content of the invention.
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