JP2004231947A - Phosphor layer-forming solution - Google Patents
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- JP2004231947A JP2004231947A JP2003434786A JP2003434786A JP2004231947A JP 2004231947 A JP2004231947 A JP 2004231947A JP 2003434786 A JP2003434786 A JP 2003434786A JP 2003434786 A JP2003434786 A JP 2003434786A JP 2004231947 A JP2004231947 A JP 2004231947A
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本発明は、発光デバイス用の蛍光体を含む蛍光体層形成用液に関するものである。さらに詳しくは、本発明は、蛍光体粒子と無機系被膜形成液とを含む、上記蛍光体層形成用液に関する。 The present invention relates to a phosphor layer forming liquid containing a phosphor for a light emitting device. More specifically, the present invention relates to the above-mentioned liquid for forming a phosphor layer, comprising the phosphor particles and a liquid for forming an inorganic film.
従来、発光素子から放出された光を蛍光材料により波長変換し、所望の発光色を得ようとする発光デバイスが提案されている。例えば粒子状の蛍光体を分散させた樹脂製の封止部材（蛍光層）で発光素子を被覆した発光デバイスが特開２００１−２１７４６６に提案されている。
また、樹脂の代わりに無機材料を用い、そこに蛍光体を分散させることが提案されている（同じく特開２００１−２１７４６６、段落番号００１５等参照）。
特開平１１−２０４８３８では、固形ガラス層を形成する塗布型ガラス材料またはセラミック前駆体ポリマーに蛍光体を分散させ、発光素子上に蛍光体含有ガラス層を形成している。
さらに、特開２００２−１８８０８５では、蛍光体粒子をポリオルガノシロキサンで被覆した蛍光体を作製し、疎水溶媒中でも分散性が優れるようにした蛍光体膜形成用塗布液も提案されている。
2. Description of the Related Art Conventionally, a light emitting device has been proposed in which light emitted from a light emitting element is wavelength-converted by a fluorescent material to obtain a desired emission color. For example, Japanese Patent Application Laid-Open No. 2001-217466 proposes a light emitting device in which a light emitting element is covered with a resin sealing member (fluorescent layer) in which a particulate phosphor is dispersed.
Further, it has been proposed to use an inorganic material instead of a resin and disperse a phosphor therein (see also JP-A-2001-217466, paragraph 0015 and the like).
In JP-A-11-204838, a phosphor is dispersed in a coating type glass material or a ceramic precursor polymer for forming a solid glass layer, and a phosphor-containing glass layer is formed on a light emitting element.
Further, Japanese Patent Application Laid-Open No. 2002-188085 proposes a coating liquid for forming a phosphor film, in which a phosphor in which phosphor particles are coated with a polyorganosiloxane is prepared so as to have excellent dispersibility even in a hydrophobic solvent.
発光デバイス用蛍光体層を形成するために、従来から樹脂に蛍光体を配合したものが用いられてきた。蛍光体を樹脂に多量に配合すると蛍光体配合樹脂の粘度が高くなりすぎて加工性に不都合を生じるため、蛍光体の量を減らし、その代わりに蛍光体配合樹脂をデバイス上に厚く塗ることにより色相を合わせていた。しかし、この方法では樹脂層が厚いため部分的に光の通過距離に相違が生じ、色相のずれが生じやすいという問題があった。また、輝度を上げるため電流を多く流すと、それによる発熱により樹脂の劣化が促進されるという問題もあった。
特開２００１−２１７４６６では、蛍光層を形成する樹脂には吸湿性があるので、水分による蛍光体の劣化回避が充分に行えなかった。
特開２００１−２１７４６６において樹脂の代わりに無機材料を用いる場合及び特開平１１−２０４８３８では蛍光体の耐環境性を上げる目的でガラス層中に蛍光体を混入させているため、ガラス層に混入できる蛍光体粒子の量は必然的に制限され、充分な蛍光を得るのに必要な蛍光体を確保するため、ガラス層が厚くなってしまう。
特開２００２−１８８０８５ではこうしてできたその蛍光体粒子をさらに水及び／または有機溶媒に分散させ塗布液をつくるという、多くの工程を必要とする。さらに、これらの方法では３次元形状の蛍光体層を量産性良く、かつ高い寸法精度でモールド成形することは不可能であった。
In order to form a phosphor layer for a light emitting device, a resin in which a phosphor is blended has conventionally been used. If a large amount of phosphor is mixed with the resin, the viscosity of the phosphor-containing resin becomes too high, which causes inconvenience in processability.Thus, reduce the amount of phosphor and instead apply a thicker layer of the phosphor-containing resin on the device. Hue was matched. However, in this method, there is a problem that the thickness of the resin layer causes a partial difference in the light transmission distance, and a hue shift easily occurs. Further, when a large amount of current is applied to increase the luminance, there is a problem that the heat generated thereby accelerates the deterioration of the resin.
In Japanese Patent Application Laid-Open No. 2001-217466, the resin forming the fluorescent layer has a hygroscopic property, so that the deterioration of the phosphor due to moisture cannot be sufficiently avoided.
In JP-A-2001-217466, when an inorganic material is used instead of a resin, and in JP-A-11-204838, a phosphor is mixed in a glass layer for the purpose of improving the environmental resistance of the phosphor, so that the phosphor can be mixed in the glass layer. The amount of the phosphor particles is necessarily limited, and the glass layer becomes thick in order to secure the phosphor necessary to obtain sufficient fluorescence.
Japanese Patent Application Laid-Open No. 2002-188085 requires many steps of dispersing the phosphor particles thus formed in water and / or an organic solvent to prepare a coating solution. Furthermore, it is impossible with these methods to mold a three-dimensional phosphor layer with good mass productivity and high dimensional accuracy.
上記問題点を解決するため、
ａ）蛍光体粒子とｂ）無機系被膜形成液、好ましくは、Ｍm+（ＯＲ1）nＲ2 m-nの加水分解・重縮合物を含む、発光デバイス用蛍光体層形成用液とした。
本発明においては無機系被膜形成液を採用するが、無機系被膜形成液は粘度が低いので、多量の蛍光体の配合が可能となる。この結果、蛍光体層を薄くすることができ、色相のずれの問題を回避することができる。
To solve the above problems,
A liquid for forming a phosphor layer for a light-emitting device, comprising a) a phosphor particle and b) an inorganic coating film forming solution, preferably a hydrolysis / polycondensate of M m + (OR 1 ) n R 2 mn .
In the present invention, an inorganic film forming liquid is employed, but since the viscosity of the inorganic film forming liquid is low, a large amount of phosphor can be blended. As a result, the thickness of the phosphor layer can be reduced, and the problem of hue shift can be avoided.
本発明において、無機系被膜形成液とは、焼成された際に蛍光体の粒子同士を連結する透光性無機連結層を形成する無機系化合物を含む液体を意味する。
本発明において用いられる無機系被膜形成液としては、式（１）で表される化合物の加水分解・重縮合物を含む無機系被膜形成液が含まれる。
Ｍm+（ＯＲ1）nＲ2 m-n （１）
（式中、Ｍは、Ｓｉ、Ａｌ、Ｚｒ及びＴｉからなる群から選択される少なくとも１種の元素であり；Ｒ1は炭素数１〜５個の炭化水素基、アルコキシアルキル基、又はアシル基であり；Ｒ2はビニル、アミノ、イミノ、エポキシ、アクリロイルオキシ、メタクリロイルオキシ、フェニル、メルカプト及びアルキル基からなる群から選択される少なくとも１種の有機基であり；ｍはＭの価数を表し；ｎはＯＲ1基の数を表し；ｍ及びｎはいずれも整数であり；ｍ≧ｎである。）
In the present invention, the inorganic coating film forming liquid means a liquid containing an inorganic compound that forms a translucent inorganic connecting layer that connects phosphor particles when fired.
The inorganic film forming liquid used in the present invention includes an inorganic film forming liquid containing a hydrolysis / polycondensate of the compound represented by the formula (1).
M m + (OR 1 ) n R 2 mn (1)
(Wherein, M is at least one element selected from the group consisting of Si, Al, Zr and Ti; R 1 is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an acyl group. R 2 is at least one organic group selected from the group consisting of vinyl, amino, imino, epoxy, acryloyloxy, methacryloyloxy, phenyl, mercapto and alkyl groups; and m represents a valence of M N represents the number of OR 1 groups; m and n are both integers; and m ≧ n.)
上記Ｍm+（ＯＲ1）nＲ2 m-nで表される化合物のうち、ＭがＳｉである化合物としては、例えば、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリアセトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、フェニルトリメトキシシラン、フェニルトリアセトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、β−シアノエチルトリエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシランなどが挙げられ、ＭがＡｌである化合物としては、アルミニウムトリイソプロポキシド、アルミニウムｎ−ブトキシド、アルミニウムトリｔ−ブトシキド、アルミニウムトリエトキシドなどが挙げられ、ＭがＺｒである化合物としては、ジルコニウムｎ−プロポキシド、ジルコニウムｎ−ブトキシド、ジルコニウムｉ−ブトキシド、ジルコニウムｔ−ブトキシド、ジルコニウムジメタクリレートジブトキシドなどが挙げられ、ＭがＴｉである化合物としては、チタンテトライソプロポキシド、チタンテトラｎ−ブトキシド、チタンテトラｉ−ブトキシド、チタンメタクリレートトリイソプロポキシド、チタンテトラメトキシプロポキシド、チタンテトラｎ−プロポキシド、チタンテトラエトキシドなどが挙げられる。これらの化合物のうち１種類だけを用いてよいが、二種類以上を混合してもかまわない。
式（１）の化合物の加水分解・重縮合反応は、例えば特開２００１−２１４０９３に記載されているような公知の方法によって行うことができる。
加水分解・重縮合反応を行うために添加する水の量は、式（１）の化合物１モルに対して０．１モル以上が好ましい。
式（１）の化合物を加水分解・縮重合する際には、既知の触媒などを添加して加水分解・縮重合を促進しても良い。この場合、添加する触媒としては、酢酸、プロピオン酸、酪酸などの有機酸や、硝酸、塩酸、リン酸、硫酸などの無機酸を用いることができる。
Among the compounds represented by M m + (OR 1 ) n R 2 mn , compounds in which M is Si include, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and vinyltrimethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriacetoxysilane, γ-mercaptopropyltrimeth Sisilane, γ-chloropropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane , Tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like. Examples of the compound in which M is Al include aluminum triisopropoxide, aluminum n-butoxide, aluminum tri-t-butoxide, and aluminum triethoxide. Compounds wherein M is Zr include zirconium n-propoxide, zirconium n-butoxide, zirconium i-butoxide, zirconium t-butoxide, zirconium. Examples of compounds in which M is Ti include titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetra i-butoxide, titanium methacrylate triisopropoxide, titanium tetramethoxypropoxide, and titanium tetramethoxypropoxide. Tetra n-propoxide, titanium tetraethoxide and the like can be mentioned. One of these compounds may be used alone, or two or more of them may be mixed.
The hydrolysis / polycondensation reaction of the compound of the formula (1) can be performed by a known method as described in, for example, JP-A-2001-214093.
The amount of water added for performing the hydrolysis / polycondensation reaction is preferably 0.1 mol or more per 1 mol of the compound of the formula (1).
When the compound of the formula (1) is subjected to hydrolysis and polycondensation, a known catalyst may be added to promote the hydrolysis and polycondensation. In this case, as a catalyst to be added, an organic acid such as acetic acid, propionic acid, and butyric acid, and an inorganic acid such as nitric acid, hydrochloric acid, phosphoric acid, and sulfuric acid can be used.
上記Ｍm+（ＯＲ1）nＲ2 m-nの加水分解・重縮合物は、好ましくは液状である。しかし、固体状の加水分解・重縮合物でも溶媒添加により液状となるものであれば使用することができる。Ｍは好ましくはＳｉである。
蛍光体粒子ａ）に対する無機系被膜形成液ｂ）の重量比は、蛍光体層形成用液をモールド成形による蛍光体層の作製に用いる場合には３以下が、蛍光体層形成用液を塗布液として用いる場合には１以下がそれぞれ好ましい。
The hydrolysis / polycondensate of M m + (OR 1 ) n R 2 mn is preferably liquid. However, a solid hydrolysis / polycondensate can be used as long as it becomes liquid by the addition of a solvent. M is preferably Si.
The weight ratio of the inorganic coating film forming solution b) to the phosphor particles a) is 3 or less when the phosphor layer forming solution is used for forming the phosphor layer by molding, and the phosphor layer forming solution is applied. When used as a liquid, 1 or less is preferred.
例えば、無機系蛍光体として、以下のものを採用することができる。例えば、赤色系の発光色を有する６ＭｇＯ・Ａｓ2Ｏ5：Ｍｎ4+、Ｙ（ＰＶ）Ｏ4：Ｅｕ、ＣａＬａ0.1Ｅｕ0.9Ｇａ3Ｏ7、ＢａＹ0.9Ｓｍ0.1Ｇａ3Ｏ7、Ｃａ（Ｙ0.5Ｅｕ0.5）（Ｇａ0.6Ｉｎ0.5）3Ｏ7、Ｙ3Ｏ3：Ｅｕ、ＹＶＯ4：Ｅｕ、Ｙ2Ｏ2：Ｅｕ、３．５ＭｇＯ・０．５ＭｇＦ2ＧｅＯ2：Ｍｎ4+及び（Ｙ・Ｃｄ）ＢＯ2：Ｅｕ等、緑色系の発光色を有するＹ3Ａｌ5Ｏ12：Ｃｅ3+（ＹＡＧ）、Ｙ2ＳｉＯ6：Ｃｅ3+、Ｔｂ3+、Ｓｒ2Ｓｉ3Ｏ8・２ＳｒＣｌ2：Ｅｕ、ＢａＭｇ2Ａｌ16Ｏ27：Ｅｕ2+，Ｍｎ2+、ＺｎＳｉＯ4：Ｍｎ、Ｚｎ2ＳｉＯ4：Ｍｎ、ＬａＰＯ4：Ｔｂ、ＳｒＡｌ2Ｏ4：Ｅｕ、ＳｒＬａ0.2Ｔｂ0.8Ｇａ3Ｏ7、ＣａＹ0.9Ｐｒ0.1Ｇａ3Ｏ7、ＺｎＧｄ0.8Ｈｏ0.2Ｇａ3Ｏ7、ＳｒＬａ0.6Ｔｂ0.4Ａｌ3Ｏ7、ＺｎＳ：Ｃｕ，Ａｌ、（Ｚｎ，Ｃｄ）Ｓ：Ｃｕ，Ａｌ、ＺｎＳ：Ｃｕ，Ａｕ，Ａｌ、Ｚｎ2ＳｉＯ4：Ｍｎ、ＺｎＳｉＯ4：Ｍｎ、ＺｎＳ：Ａｇ，Ｃｕ、（Ｚｎ・Ｃｄ）Ｓ：Ｃｕ、ＺｎＳ：Ｃｕ、ＧｄＯＳ：Ｔｂ、ＬａＯＳ：Ｔｂ、ＹＳｉＯ4：Ｃｅ・Ｔｂ、ＺｎＧｅＯ4：Ｍｎ、ＧｅＭｇＡｌＯ：Ｔｂ、ＳｒＧａＳ：Ｅｕ2+、ＺｎＳ：Ｃｕ・Ｃｏ、ＭｇＯ・ｎＢ2Ｏ3：Ｇｅ，Ｔｂ、ＬａＯＢｒ：Ｔｂ，Ｔｍ、及びＬａ2Ｏ2Ｓ：Ｔｂ等、青色系の発光色を有する（Ｂａ，Ｃａ，Ｍｇ）6（ＰＯ4）3Ｃｌ：Ｅｕ2+、（Ｂａ，Ｍｇ）2Ａｌ16Ｏ27：Ｅｕ2+、Ｂａ3ＭｇＳｉ2Ｏ8：Ｅｕ2+、ＢａＭｇ2Ａｌ16Ｏ27：Ｅｕ2+、（Ｓｒ，Ｃａ）10（ＰＯ4）6Ｃｌ2：Ｅｕ2+、（Ｓｒ，Ｃａ）10（ＰＯ4）6Ｃｌ2・ｎＢ2Ｏ3：Ｅｕ2+、Ｓｒ10（ＰＯ4）6Ｃｌ2：Ｅｕ2+、（Ｓｒ，Ｂａ，Ｃａ）5（ＰＯ4）3Ｃｌ：Ｅｕ2+、Ｓｒ2Ｐ2Ｏ7：Ｅｕ、Ｓｒ5（ＰＯ4）3Ｃｌ：Ｅｕ、（Ｓｒ，Ｃａ，Ｂａ）3（ＰＯ4）6Ｃｌ：Ｅｕ、ＳｒＯ・Ｐ2Ｏ5・Ｂ2Ｏ5：Ｅｕ、（ＢａＣａ）5（ＰＯ4）3Ｃｌ：Ｅｕ、ＳｒＬａ0.85Ｔｍ0.06Ｇａ3Ｏ7、ＺｎＳ：Ａｇ、ＧａＷＯ4、Ｙ3ＳｉＯ6：Ｃｅ、ＺｎＳ：Ａｇ、Ｇａ，Ｃｌ、Ｃａ2Ｂ4ＯＣｌ：Ｅｕ2+、ＢａＭｇＡｌ4Ｏ3：Ｅｕ2+、及び一般式（Ｍ１，Ｅｕ）10（ＰＯ4）6Ｃｌ2（Ｍ１は、Ｍｇ，Ｃａ，Ｓｒ，及びＢａからなる群から選択される少なくとも１種の元素）で表される蛍光体等、を用いることができる。また、白色系の発光色を有するＹＶＯ4：Ｄｙ、黄色系の発光色を有するＣａＬｕ0.5Ｄｙ0.5Ｇａ3Ｏ7を用いることもできる。
発光素子からの光の波長が４００ｎｍ以下のいわゆる紫外線であった場合、例えば、ＺｎＳ：Ｃｕ，Ａｌ、（Ｚｎ，Ｃｄ）Ｓ：Ｃｕ，Ａｌ、ＺｎＳ：Ｃｕ，Ａｕ，Ａｌ、Ｙ2ＳｉＯ6：Ｔｂ（Ｚｎ，Ｃｄ）Ｓ：Ｃｕ、Ｇｄ2Ｏ2Ｓ：Ｔｂ、Ｙ2Ｏ2Ｓ：Ｔｂ、Ｙ3Ａｌ5Ｏ12：Ｃｅ、（Ｚｎ，Ｃｄ）Ｓ：Ａｇ、ＺｎＳ：Ａｇ，Ｃｕ，Ｇａ，Ｃｌ、Ｙ3Ａｌ5Ｏ12：Ｔｂ、Ｙ3（Ａｌ，Ｇａ）6Ｏ12：Ｔｂ、Ｚｎ2ＳｉＯ4：Ｍｎ、ＬａＰＯ4：Ｃｅ，Ｔｂ、Ｙ2Ｏ3Ｓ：Ｅｕ、ＹＶＯ4：Ｅｕ、ＺｎＳ：Ｍｎ、Ｙ2Ｏ3：Ｅｕ、ＺｕＳ：Ａｇ、ＺｎＳ：Ａｇ，Ａｌ、（Ｓｒ，Ｃａ，Ｂａ，Ｍｇ）10（ＰＯ4）6Ｃｌ2：Ｅｕ、Ｓｒ10（ＰＯ4）6Ｃｌ2：Ｅｕ、（Ｂａ，Ｓｒ，Ｅｕ）（Ｍｇ，Ｍｎ）Ａｌ10Ｏ17、（Ｂａ，Ｅｕ）ＭｇＡｌ10Ｏ17、ＺｎＯ：Ｚｎ、Ｙ2ＳｉＯ5：Ｃｅのいずれか又はこれらの中から選ばれる二以上の蛍光体を組み合わせて用いることができる。
これらの粒子の粒径は特に限定されないが、好ましくは１００ｎｍから１０μｍのオーダーである。また、粒子の形状も、蛍光体層形成用液の流動性に影響を与えない限り、特に限定されない。
For example, the following can be adopted as the inorganic phosphor. For example, 6MgO · As 2 O 5 with luminescent color of red: Mn 4+, Y (PV) O 4: Eu, CaLa 0.1 Eu 0.9 Ga 3 O 7, BaY 0.9 Sm 0.1 Ga 3 O 7, Ca (Y 0.5 Eu 0.5) (Ga 0.6 In 0.5) 3 O 7, Y 3 O 3: Eu, YVO 4: Eu, Y 2 O 2: Eu, 3.5MgO · 0.5MgF 2 GeO 2: Mn 4+ and (Y · Cd) BO 2: Eu or the like, Y 3 Al 5 O 12 with luminescent color greenish: Ce 3+ (YAG), Y 2 SiO 6: Ce 3+, Tb 3+, Sr 2 Si 3 O 8 · 2SrCl 2 : Eu, BaMg 2 Al 16 O 27 : Eu 2+ , Mn 2+ , ZnSiO 4 : Mn, Zn 2 SiO 4 : Mn, LaPO 4 : Tb, SrAl 2 O 4 : Eu, SrLa 0.2 Tb 0.8 Ga 3 O 7, CaY 0.9 Pr 0.1 Ga 3 O 7, ZnGd 0.8 Ho 0.2 Ga 3 O 7, SrLa 0.6 T 0.4 Al 3 O 7, ZnS: Cu, Al, (Zn, Cd) S: Cu, Al, ZnS: Cu, Au, Al, Zn 2 SiO 4: Mn, ZnSiO 4: Mn, ZnS: Ag, Cu, ( Zn · Cd) S: Cu, ZnS: Cu, GdOS: Tb, LaOS: Tb, YSiO 4: Ce · Tb, ZnGeO 4: Mn, GeMgAlO: Tb, SrGaS: Eu 2+, ZnS: Cu · Co, MgO · (Ba, Ca, Mg) 6 (PO 4 ) 3 Cl: Eu 2+ having a blue emission color, such as nB 2 O 3 : Ge, Tb, LaOBr: Tb, Tm, and La 2 O 2 S: Tb. , (Ba, Mg) 2 Al 16 O 27 : Eu 2+ , Ba 3 MgSi 2 O 8 : Eu 2+ , BaMg 2 Al 16 O 27 : Eu 2+ , (Sr, Ca) 10 (PO 4 ) 6 Cl 2: Eu 2+, (Sr, Ca) 10 (PO 4) 6 Cl 2 · B 2 O 3: Eu 2+, Sr 10 (PO 4) 6 Cl 2: Eu 2+, (Sr, Ba, Ca) 5 (PO 4) 3 Cl: Eu 2+, Sr 2 P 2 O 7: Eu , Sr 5 (PO 4) 3 Cl: Eu, (Sr, Ca, Ba) 3 (PO 4) 6 Cl: Eu, SrO · P 2 O 5 · B 2 O 5: Eu, (BaCa) 5 (PO 4 ) 3 Cl: Eu, SrLa 0.85 Tm 0.06 Ga 3 O 7 , ZnS: Ag, GaWO 4 , Y 3 SiO 6 : Ce, ZnS: Ag, Ga, Cl, Ca 2 B 4 OCl: Eu 2+ , BaMgAl 4 O 3 : Eu 2+ , and represented by the general formula (M1, Eu) 10 (PO 4 ) 6 Cl 2 (M1 is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba) Phosphors and the like can be used. Alternatively, YVO 4 : Dy having a white emission color and CaLu 0.5 Dy 0.5 Ga 3 O 7 having a yellow emission color can be used.
When the wavelength of light from the light emitting element is so-called ultraviolet light of 400 nm or less, for example, ZnS: Cu, Al, (Zn, Cd) S: Cu, Al, ZnS: Cu, Au, Al, Y 2 SiO 6 : Tb (Zn, Cd) S: Cu, Gd 2 O 2 S: Tb, Y 2 O 2 S: Tb, Y 3 Al 5 O 12: Ce, (Zn, Cd) S: Ag, ZnS: Ag, Cu, Ga, Cl, Y 3 Al 5 O 12 : Tb, Y 3 (Al, Ga) 6 O 12 : Tb, Zn 2 SiO 4 : Mn, LaPO 4 : Ce, Tb, Y 2 O 3 S: Eu, YVO 4 : Eu, ZnS: Mn, Y 2 O 3 : Eu, ZuS: Ag, ZnS: Ag, Al, (Sr, Ca, Ba, Mg) 10 (PO 4 ) 6 Cl 2 : Eu, Sr 10 (PO 4 ) 6 Cl 2 : Eu, (Ba, Sr, Eu) (Mg, Mn) Al 10 O 17 , (Ba, Eu) MgAl Any of 10 O 17 , ZnO: Zn, Y 2 SiO 5 : Ce, or two or more phosphors selected from these can be used in combination.
The particle size of these particles is not particularly limited, but is preferably on the order of 100 nm to 10 μm. Also, the shape of the particles is not particularly limited as long as it does not affect the fluidity of the phosphor layer forming liquid.
蛍光体層形成用液を上記を満たすものとすることで、この蛍光体層形成用液を用いて作製する蛍光体層は蛍光体の粒子自体を薄い透光性無機系連結層で連結し実質的に蛍光体粒子同士が連結するようになる。これにより蛍光体層中に蛍光体粒子が均一かつ密に充てんされた状態となり、単位体積当たりの蛍光体量が最大となる。よって薄い蛍光層によっても充分な蛍光を取り出すことが可能となり発光素子からの光を高い効率で波長変換できるとともに、蛍光の波長スペクトルも安定して色むら等の発生を未然に防止できる。さらに蛍光体層中の蛍光体粒子表面は透光性無機系連結層の薄い膜で全体が覆われており、保護膜の機能も同時に果たす。また、この蛍光体層形成用液は蛍光体粒子と液状加水分解重縮合物を混合するというだけで蛍光体粒子表面を前処理する必要もなく、容易に塗布液として使用することができる。
さらにはこの蛍光体層形成用液は蛍光体の占める割合が高くかつ流動性もあるため、モールド成形による蛍光体層の作製が可能となり、量産性良く、高い寸法精度で３次元形状の蛍光体層を得ることができる。すなわち、予めモールド成形によって蛍光体層を作製しておくと、これをデバイスにかぶせるだけで加工が済むため、生産性が改善すると共に、色相のばらつきも安定化するという利点がある。かかる態様で使用する場合、必要により、成形性を向上させるために、Ａｌ2Ｏ3、ＴｉＯ2、ＳｉＯ2粒子等の無機粒子を添加することができる。これらの粒子の粒径は１００μｍ以下が好ましい。
なお、蛍光体の中には加水分解性のものもあるが、本発明に係る無機系被膜形成液の加水分解・重縮合物を脱水・脱アルコール処理を行ってから使用すれば、そのような蛍光体との併用が容易となる利点もある。
以上のように、本発明の蛍光体層形成用液は上述の従来の問題点をすべて解決するものである。
By making the phosphor layer forming solution satisfy the above, the phosphor layer produced using this phosphor layer forming solution is substantially formed by connecting the phosphor particles themselves with a thin translucent inorganic connection layer. As a result, the phosphor particles are connected to each other. Thereby, the phosphor layer is uniformly and densely filled in the phosphor layer, and the amount of the phosphor per unit volume is maximized. Therefore, a sufficient fluorescent light can be taken out even with a thin fluorescent layer, the wavelength of the light from the light emitting element can be converted with high efficiency, and the wavelength spectrum of the fluorescent light can be stably prevented to prevent the occurrence of color unevenness or the like. Further, the surface of the phosphor particles in the phosphor layer is entirely covered with a thin film of the light-transmitting inorganic connection layer, and simultaneously functions as a protective film. In addition, the phosphor layer forming liquid can be easily used as a coating liquid without mixing the phosphor particles and the liquid hydrolyzed polycondensate, thereby eliminating the need for pretreatment of the phosphor particle surfaces.
Further, since the phosphor layer forming liquid has a high ratio of the phosphor and has fluidity, the phosphor layer can be formed by molding, and the phosphor of the three-dimensional shape can be mass-produced with high dimensional accuracy. Layers can be obtained. In other words, if the phosphor layer is prepared in advance by molding, the process can be completed simply by covering the device with the phosphor layer, so that there is an advantage that productivity is improved and variation in hue is stabilized. When used in such an embodiment, if necessary, inorganic particles such as Al 2 O 3 , TiO 2 , and SiO 2 particles can be added to improve the moldability. The particle size of these particles is preferably 100 μm or less.
In addition, some of the phosphors are hydrolyzable, but if the hydrolyzate / polycondensate of the inorganic coating film forming solution according to the present invention is used after dehydration / dealcoholization treatment, such a phosphor is used. There is also an advantage that it can be easily used in combination with a phosphor.
As described above, the phosphor layer forming liquid of the present invention solves all of the conventional problems described above.
以下に例を挙げるが、それらは本発明の説明を目的とするものであって、本発明をこれらの態様に限定することを意図するものではない。
（例１）
ビニルトリエトキシシラン５ｇに水３ｇと酢酸０．１７ｇを混合し、３時間室温で攪拌し加水分解・重縮合反応を行った。この溶液を１ｇとりそれに対しイソプロピルセロソルブ０．５ｇと黄色系蛍光体４ｇを混合し、攪拌を１時間行った。この塗布液を発光素子上に塗布、２００℃で１０分間乾燥したところ、蛍光体層が形成できた。さらにこの蛍光体層は４００℃で１０分間焼成されたが、どちらの場合も白色系の出力光が得られた。
（例２）
例１で得られた塗布液を成形型に入れ、成形した。代表的な成形形状は図１に示すようなものである。その後２００℃１０分間乾燥後も成形後の形状を保っていた。
４００℃１０分間焼成後の成型品は割れることはなかった。この成型品を青色発光素子上にのせ、発光素子全体を被ったところ、白色系の出力光が得られた。
（例３）
メチルトリメトキシシラン１３．６ｇに水３．６ｇと酢酸０．６ｇを混合し、２４時間室温で攪拌し加水分解・重縮合反応を行った。この溶液１ｇを採り、それに黄色系蛍光体３ｇを混合した。この液を成形型に入れ、２００℃で１０分間乾燥し、成形した。成形形状は図１参照。この成形品をさらに４００℃で１０分間焼成したが、成形品には割れ、変色等の発生はなかった。こうして得られた成形品を青色発光素子上に乗せ、発光素子全体を被ったところ、白色の出力光が得られた。
The following are examples, which are intended to illustrate the present invention and are not intended to limit the present invention to these embodiments.
(Example 1)
3 g of water and 0.17 g of acetic acid were mixed with 5 g of vinyltriethoxysilane, and the mixture was stirred at room temperature for 3 hours to carry out a hydrolysis / polycondensation reaction. 1 g of this solution was mixed with 0.5 g of isopropyl cellosolve and 4 g of a yellow phosphor, and the mixture was stirred for 1 hour. This coating solution was applied on a light emitting element and dried at 200 ° C. for 10 minutes, whereby a phosphor layer was formed. Further, this phosphor layer was baked at 400 ° C. for 10 minutes, and in each case, white output light was obtained.
(Example 2)
The coating liquid obtained in Example 1 was placed in a mold and molded. A typical molding shape is as shown in FIG. Thereafter, the shape after molding was maintained even after drying at 200 ° C. for 10 minutes.
The molded product after firing at 400 ° C. for 10 minutes did not crack. When this molded product was placed on a blue light emitting element and covered the entire light emitting element, white output light was obtained.
(Example 3)
3.6 g of water and 0.6 g of acetic acid were mixed with 13.6 g of methyltrimethoxysilane, and the mixture was stirred at room temperature for 24 hours to perform a hydrolysis / polycondensation reaction. 1 g of this solution was taken and mixed with 3 g of a yellow phosphor. This liquid was placed in a mold, dried at 200 ° C. for 10 minutes, and molded. See FIG. 1 for the molding shape. The molded article was further baked at 400 ° C. for 10 minutes, and no crack, discoloration, etc. occurred in the molded article. The molded article thus obtained was placed on a blue light-emitting element, and when the entire light-emitting element was covered, white output light was obtained.
本発明の蛍光体層形成用液は発光素子上に塗布、乾燥するだけで容易に無機系の蛍光体層を形成することを可能にした。また、本発明の蛍光体層形成用液から得られた無機系蛍光体層は薄い透光性無機系連結層で蛍光体粒子同士を連結した構造となるため、単位体積当たりの蛍光体量が多くなる。
従って、薄い蛍光体層によっても充分な蛍光を取り出すことが可能となる。
さらに本発明の蛍光体層形成用液はモールド成形による蛍光体層形成も可能とし、３次元形状の蛍光体層を量産性高く、かつ寸法精度良く作製できるという効果も得られた。
The liquid for forming a phosphor layer of the present invention can easily form an inorganic phosphor layer simply by coating and drying on a light emitting element. In addition, since the inorganic phosphor layer obtained from the phosphor layer forming liquid of the present invention has a structure in which phosphor particles are connected by a thin translucent inorganic connection layer, the amount of phosphor per unit volume is reduced. More.
Therefore, it is possible to take out sufficient fluorescence even with a thin phosphor layer.
Furthermore, the phosphor layer forming liquid of the present invention can also form a phosphor layer by molding, and has the effect of producing a three-dimensionally shaped phosphor layer with high mass productivity and dimensional accuracy.
Claims (5)
Ｍm+（ＯＲ1）nＲ2 m-n
（式中、ＭはＳｉ、Ａｌ、Ｚｒ及びＴｉからなる群から選択される少なくとも１種の元素であり；ｍはＭの価数を表わし；Ｒ1は炭素数１〜５の炭化水素基、アルコキシアルキル基またはアシル基であり；Ｒ2はビニル、アミノ、イミノ、エポキシ、アクリロイルオキシ、メタクリロイルオキシ、フェニル、メルカプト及びアルキル基からなる群から選択される少なくとも１種の有機基であり；ｎはＯＲ1基の数を表し；ｍ及びｎはいずれも整数であり；ｍ≧ｎである。）
で表わされる化合物の加水分解・重縮合物を含む、請求項１記載の液。 Inorganic film forming liquid,
M m + (OR 1 ) n R 2 mn
(Wherein, M is at least one element selected from the group consisting of Si, Al, Zr and Ti; m represents a valence of M; R 1 represents a hydrocarbon group having 1 to 5 carbon atoms; R 2 is at least one organic group selected from the group consisting of vinyl, amino, imino, epoxy, acryloyloxy, methacryloyloxy, phenyl, mercapto and alkyl groups; n is It represents the number of oR 1 group; m and n are both an integer; a m ≧ n).
The liquid according to claim 1, comprising a hydrolysis / polycondensate of the compound represented by the formula:
The liquid according to any one of claims 1 to 4, wherein the inorganic film forming liquid has a light-transmitting property after firing.
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