JP2002129157A - Blue pigment-attaching fluorescent substance - Google Patents
Blue pigment-attaching fluorescent substanceInfo
- Publication number
- JP2002129157A JP2002129157A JP2000370755A JP2000370755A JP2002129157A JP 2002129157 A JP2002129157 A JP 2002129157A JP 2000370755 A JP2000370755 A JP 2000370755A JP 2000370755 A JP2000370755 A JP 2000370755A JP 2002129157 A JP2002129157 A JP 2002129157A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- pigment
- blue
- blue pigment
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- Luminescent Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、表面に青色顔料を
付着した、カラーＴＶ及びコンピューターディスプレイ
用のカラーブラウン管（カラーＣＲＴ）に使用される顔
料付蛍光体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigmented phosphor having a blue pigment adhered to the surface and used for a color cathode ray tube (color CRT) for a color TV and a computer display.
【０００２】[0002]
【従来の技術】カラーＣＲＴ等の蛍光面に蛍光体を使用
したディスプレイの画面の明るさを出来るだけ低下させ
ずにコントラストを改善するために、その蛍光体の発光
色に類似の体色を有する顔料粒子を表面に付着させた、
顔料付き蛍光体を用いる方法が有効で、ほとんどのカラ
ーＣＲＴの蛍光面に採用されており、特に近年、顔料の
付着量を増加させてＣＲＴの管面反射率を低下させた管
種が多くなってきている。2. Description of the Related Art In order to improve contrast without decreasing the brightness of the screen of a display such as a color CRT using a phosphor on a phosphor screen, the phosphor has a body color similar to the emission color of the phosphor. Pigment particles attached to the surface,
A method using a phosphor with a pigment is effective, and is adopted for most color CRT phosphor screens. In recent years, in particular, in recent years, the number of tube types in which the amount of pigment attached has been reduced to reduce the CRT tube surface reflectance has increased. Is coming.
【０００３】このような状況は青色顔料付青色発光蛍光
体においても同様であり、その場合、顔料の使用量を多
くすることになるので顔料が蛍光体に対して強固に付着
していないと蛍光体をＣＲＴのガラス面に塗布して蛍光
面を形成する工程において顔料が分離し、顔料ムラが生
じたり、蛍光体の反射率が上がって所望のコントラスト
が得られなかったりするため、多量の顔料を付着させて
もより強固に顔料粒子が付着する青色顔料付蛍光体が要
望されている。[0003] Such a situation is the same for a blue light-emitting phosphor with a blue pigment. In this case, the amount of the pigment used increases, and if the pigment is not firmly attached to the phosphor, the fluorescent light will not be emitted. In the process of applying the body to the glass surface of the CRT to form a phosphor screen, the pigments are separated, causing pigment unevenness, or increasing the reflectance of the phosphor, so that a desired contrast cannot be obtained. There is a demand for a phosphor with a blue pigment to which the pigment particles adhere more firmly even when the phosphor is adhered.
【０００４】ところで、蛍光体表面に顔料粒子を付着さ
せる場合、顔料粒子の付着工程は通常は蛍光体の水スラ
リー中においてなされるため、スラリー中での蛍光体の
分散性を損なわない条件で顔料を付着させる必要があ
る。そのため、顔料粒子を蛍光体に付着させるバインダ
ーとしてはゼラチン、アラビアゴム等の親水性の樹脂が
使用されているが、顔料付着量を従来の顔料付蛍光体よ
りも多くする必要上、使用されるバインダー量を増やす
と水スラリー中での蛍光体の分散性が悪くなるという問
題があった。In the case where pigment particles are adhered to the surface of the phosphor, the pigment particles are usually attached in a water slurry of the phosphor, so that the pigment is dispersed under conditions that do not impair the dispersibility of the phosphor in the slurry. Must be attached. Therefore, a hydrophilic resin such as gelatin or gum arabic is used as a binder for attaching pigment particles to the phosphor, but is used because the pigment attachment amount needs to be larger than that of a conventional pigmented phosphor. When the amount of the binder is increased, there is a problem that the dispersibility of the phosphor in the water slurry is deteriorated.
【０００５】また、顔料付蛍光体用の青色顔料として主
として用いられているコバルトブルーは一般にはその粒
子径が０．２〜０．５μｍであり、使用に際してこれを
ボールミル等を用いて粉砕、分散化処理したものもせい
ぜい０．２〜０．３μｍ程度であって、この程度の粒子
径の顔料粒子を蛍光体表面に付着させると顔料付蛍光体
粒子表面の凹凸が大きくなり、表面の平滑な蛍光体の場
合に比べて外部からの機械的な力を受けやすくなり、そ
のためにやはり多量の顔料を付着させた場合には顔料粒
子の付着力が不十分であった。[0005] Cobalt blue, which is mainly used as a blue pigment for a phosphor with a pigment, generally has a particle size of 0.2 to 0.5 µm, and when used, is crushed and dispersed using a ball mill or the like. The surface of the pigmented phosphor particles is also about 0.2 to 0.3 μm at most, and when pigment particles having such a particle diameter are adhered to the phosphor surface, the irregularities on the surface of the phosphor particles with pigment become large and the surface becomes smooth. As compared with the case of the fluorescent substance, mechanical force from the outside is easily received. Therefore, when a large amount of pigment is adhered, the adhesive force of the pigment particles is insufficient.
【０００６】[0006]
【発明が解決使用とする課題】本発明は上記状況に鑑み
てなされたもので、コバルトブルー青色顔料粒子を付着
した顔料付青色発光蛍光体において、顔料の付着力が強
く、従来の顔料付蛍光体に比べて顔料付着量が多くても
顔料剥離の少ない高コントラストの顔料付蛍光体を提供
することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is intended to provide a pigmented blue light-emitting phosphor to which cobalt blue pigment particles are adhered. It is an object of the present invention to provide a high-contrast pigmented phosphor having a small amount of pigment detachment even if the amount of pigment attached is large as compared with a body.
【０００７】[0007]
【課題を解決するための手段】本発明者等は上記目的達
成のため、主として使用する顔料粒子の粒子径及びその
付着のさせ方等について詳細に検討した結果、使用する
コバルトブルー青色顔料として特定粒子径以下の超微粒
子であり、しかも良く分散された顔料粒子を用いること
によって上記目的を達成し得ることが分かった。本発明
の青色顔料付蛍光体は下記の構成からなる。Means for Solving the Problems To achieve the above object, the present inventors have studied in detail the particle size of the pigment particles to be used and how to make them adhere, and as a result, the pigment has been identified as the cobalt blue blue pigment to be used. It has been found that the above object can be achieved by using pigment particles which are ultrafine particles having a particle size equal to or less than the particle size and are well dispersed. The phosphor with a blue pigment of the present invention has the following constitution.
【０００８】（１）青色発光蛍光体の表面に平均粒子径
が０．１μｍ以下のコバルトブルーからなる青色顔料粒
子が付着していることを特徴とする青色顔料付蛍光体。 （２）前記青色顔料粒子の平均粒子径が０．０１〜０．
１μｍであることを特徴とする前記（１）に記載の青色
顔料付蛍光体。 （３）前記青色顔料粒子がバインダーを介して前記青色
発光蛍光体の表面に付着していることを特徴とする前記
（１）ないし（２）に記載の青色顔料付蛍光体。 （４）前記バインダーが天然樹脂、アクリル樹脂及びス
チレンブタジエン樹脂の中の少なくとも１種であること
を特徴とする前記（３）に記載の青色顔料付蛍光体。(1) A phosphor with a blue pigment, wherein blue pigment particles made of cobalt blue having an average particle diameter of 0.1 μm or less adhere to the surface of the blue light-emitting phosphor. (2) The blue pigment particles have an average particle size of 0.01 to 0.1.
The phosphor with a blue pigment according to the above (1), which is 1 μm. (3) The phosphor with a blue pigment according to (1) or (2), wherein the blue pigment particles are attached to a surface of the blue light-emitting phosphor via a binder. (4) The phosphor with a blue pigment according to (3), wherein the binder is at least one of a natural resin, an acrylic resin, and a styrene-butadiene resin.
【０００９】（５）前記天然樹脂がゼラチンであること
を特徴とする前記（４）に記載の青色顔料付蛍光体。 （６）前記バインダーの量が前記青色発光蛍光体に対し
て０．０１〜１．０重量％の範囲にあることを特徴とす
る前記（３）〜（５）に記載の青色顔料付蛍光体。 （７）前記青色顔料粒子の付着量が前記青色発光蛍光体
に対して０．３％〜１５重量％の範囲にあることを特徴
とする前記（１）〜（６）のいずれかに記載の青色顔料
付蛍光体。 （８）青色発光蛍光体の表面に、前記蛍光体に対して
１．０重量％以下のゼラチンを介してコバルトブルー青
色顔料粒子を付着させた青色顔料付蛍光体であって、前
記コバルトブルー青色顔料粒子の平均粒子径が０．１μ
ｍより大である外は組成が同一である青色顔料付蛍光体
よりも前記コバルトブルー青色顔料の剥離の程度が少な
いことを特徴とする青色顔料付蛍光体。(5) The phosphor with a blue pigment according to (4), wherein the natural resin is gelatin. (6) The phosphor with a blue pigment according to any of (3) to (5), wherein the amount of the binder is in the range of 0.01 to 1.0% by weight based on the blue light-emitting phosphor. . (7) The method according to any one of (1) to (6), wherein the adhesion amount of the blue pigment particles is in a range of 0.3% to 15% by weight based on the blue light-emitting phosphor. Phosphor with blue pigment. (8) A phosphor with a blue pigment having cobalt blue blue pigment particles adhered to the surface of a blue light emitting phosphor via gelatin of 1.0% by weight or less with respect to the phosphor, wherein the cobalt blue blue The average particle size of the pigment particles is 0.1μ
A phosphor with a blue pigment, wherein the degree of peeling of the cobalt blue blue pigment is smaller than that of a phosphor with a blue pigment having the same composition except that it is larger than m.
【００１０】[0010]
【発明の実施の形態】以下、本発明を更に詳細に説明す
る。本発明の顔料付蛍光体は、青色発光蛍光体（青色蛍
光体）が懸濁している水等の媒体中において平均粒子径
が０．１μｍ以下である超微粒子のコバルトーブルー顔
料を適当な分散剤と共に適当な分散方法と条件で分散さ
せてから、これを凝集を起こさせないように均一に蛍光
体表面に付着させる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The phosphor with a pigment according to the present invention is obtained by appropriately dispersing an ultrafine cobalt-blue pigment having an average particle diameter of 0.1 μm or less in a medium such as water in which a blue light-emitting phosphor (blue phosphor) is suspended. After being dispersed together with the agent by an appropriate dispersing method and conditions, this is uniformly attached to the phosphor surface without causing aggregation.
【００１１】すなわち、所定量のコバルトブルー青色顔
料粒子を水中に懸濁させてスラリー化し、その中に例え
ばポリビニルアルコール（ＰＶＡ）などの分散剤を添加
し、これをアルミナ、ジルコニアなどのセラミックのメ
ディアを用いてボールミル処理して十分に分散したコバ
ルトブルー青色顔料の懸濁液を調製する。本発明におい
て使用されるコバルトブルー顔料は、その組成がＣｏＯ
−Ａｌ２Ｏ３系またはＣｏＯ−ＭｇＯ−Ａｌ２Ｏ３系で
あって青色系の体色を有する顔料であり、顔料の分散性
を低下させない程度の量のバインダーを介して蛍光体表
面に付着させた場合でも顔料の付着力を低下させないよ
うにするためには、用いる顔料としてレーザー式遠心沈
降法で測定した時の平均粒子径がほぼ０．１μｍである
超微粒子の顔料が使用される。但し、顔料粒子の粒子径
がある径以下になると顔料の化学的反応性が増して化学
的に不安定となると共に透明性が増して顔料としての機
能を有さなくなるので、平均粒子径がおよそ０．０１μ
ｍ以上であるものが好ましい。このような粒子径の超微
粒子顔料は顔料の組成、沈殿条件、焼成条件、分散条件
などを調整して製造される。That is, a predetermined amount of cobalt blue blue pigment particles are suspended in water to form a slurry, into which a dispersant such as polyvinyl alcohol (PVA) is added, and this is added to a ceramic medium such as alumina or zirconia. To prepare a well dispersed suspension of cobalt blue blue pigment by ball milling. The cobalt blue pigment used in the present invention has a composition of CoO
A pigment having a blue body color, which is an Al 2 O 3 system or a CoO—MgO—Al 2 O 3 system, adheres to the phosphor surface via a binder in such an amount that does not decrease the dispersibility of the pigment In order to prevent the adhesion of the pigment from being reduced even in the case of using the pigment, an ultrafine pigment having an average particle diameter of about 0.1 μm as measured by a laser centrifugal sedimentation method is used as the pigment to be used. However, when the particle diameter of the pigment particles is less than a certain diameter, the chemical reactivity of the pigment increases and becomes chemically unstable, and the transparency increases and the pigment does not have a function. 0.01μ
m or more is preferable. The ultrafine pigment having such a particle size is produced by adjusting the composition of the pigment, precipitation conditions, firing conditions, dispersion conditions, and the like.
【００１２】なお、顔料の粒度はその粒子の分散の程度
によって変わり、凝集を解いて分散度を高めて行くと次
第に粒度の測定値が小さくなるので、本発明のコバルト
ーブルー青色顔料の粒子径は、顔料の分散度を十分に高
め、ほぼ一次粒子になってそれ以上分散処理を行っても
それ以上測定値がほとんど変わらなくなる条件で分散処
理して求めた。即ち、粒度測定のために同一の分散顔料
スラリーから分取した複数のサンプルにそれぞれ異なる
条件（負荷）で各サンプルに超音波処理を施してその時
の粒度をそれぞれ測定し、ある一定以上の負荷を与えて
もそれ以上粒度がほとんど変化しない分散化条件を決め
て、その超音波処理条件でサンプルを分散させた時の粒
度をその顔料粒子の粒子径と見なした。The particle size of the pigment varies depending on the degree of dispersion of the particles, and the measured value of the particle size gradually decreases as the degree of dispersion is increased by disintegrating the particles. Was determined by sufficiently increasing the degree of dispersion of the pigment so as to become substantially primary particles and performing a dispersion treatment under the condition that the measured value hardly changes even if the dispersion treatment is further performed. That is, for a plurality of samples taken from the same dispersed pigment slurry for particle size measurement, each sample is subjected to ultrasonic treatment under different conditions (load), and the particle size at that time is measured, and a load exceeding a certain fixed value is applied. Dispersion conditions under which the particle size hardly changed even after the application were determined were determined, and the particle size when the sample was dispersed under the ultrasonic treatment conditions was regarded as the particle size of the pigment particles.
【００１３】一方、これとは別に、所定量の青色蛍光体
を水または温水中に懸濁させた蛍光体スラリーを調製
し、この蛍光体スラリーの中に先に調製されたコバルト
ブルー青色顔料の分散液の所定量を添加し、更にバイン
ダーとして、例えばゼラチンとアラビアゴム（以下、Ｇ
／Ａという）を添加して十分に攪拌しながら塩酸、酢酸
などの鉱酸を添加しながらスラリーのｐＨを調節してＧ
／Ａをゲル化させ、ゲル化したＧ／Ａを介してコバルト
ブルー青色顔料の微粒子を蛍光体粒子の表面に固定す
る。なお、ここで「Ｇ／Ａを介して」とは、蛍光体粒子
の表面にまず薄いＧ／Ａ層が形成されると共に、そのＧ
／Ａ層上に青色顔料粒子が付着する場合、Ｇ／Ａがゲル
化する過程で青色顔料粒子を巻き込みながら蛍光体表面
に付着する場合、先ず青色顔料粒子が蛍光体粒子表面に
付着しその上にゲル化したＧ／Ａの層が形成される場合
などをいう。本発明の青色顔料付蛍光体において使用さ
れ得るバインダーとしては、Ｇ／Ａの外にアクリル樹
脂、スチレンブタジエン樹脂等が挙げられる。On the other hand, separately from this, a phosphor slurry in which a predetermined amount of a blue phosphor is suspended in water or warm water is prepared, and the previously prepared cobalt blue blue pigment is dispersed in the phosphor slurry. A predetermined amount of the dispersion is added, and as a binder, for example, gelatin and gum arabic (hereinafter referred to as G
/ A) and adding a mineral acid such as hydrochloric acid or acetic acid while sufficiently stirring and adjusting the pH of the slurry to G.
/ A is gelled, and fine particles of the cobalt blue blue pigment are fixed on the surfaces of the phosphor particles via the gelled G / A. Here, “via G / A” means that a thin G / A layer is first formed on the surface of the phosphor particles,
When the blue pigment particles adhere to the surface of the phosphor particles while the blue pigment particles are involved in the gelation process of G / A, the blue pigment particles first adhere to the surface of the phosphor particles, And a case where a gelled G / A layer is formed. Examples of the binder that can be used in the phosphor with a blue pigment of the present invention include an acrylic resin, a styrene-butadiene resin, and the like in addition to G / A.
【００１４】この時使用されるコバルトブルー青色顔料
粒子の量は蛍光体に対して０．３〜１５重量％の範囲で
あることが好ましい。コバルトブルー青色顔料の添加量
が０．３重量％より少ないとコントラストの向上した顔
料付蛍光体とならず、１５％重量％より多く添加すると
得られる蛍光体の発光輝度が大きく低下する。また、使
用されるバインダーの量としては蛍光体に対してほぼ
０．０１〜１．０重量％程度添加される。０．０１重量
％より少ないと蛍光体と顔料粒子との付着が不十分とな
り、１．０重量％より多いと顔料の付着強度は十分とな
るが、得られた顔料付蛍光体の液媒体中での分散性が悪
くなって実用上共に好ましくない。The amount of the cobalt blue pigment particles used at this time is preferably in the range of 0.3 to 15% by weight based on the phosphor. If the addition amount of the cobalt blue blue pigment is less than 0.3% by weight, a phosphor with improved contrast is not obtained. If the addition amount is more than 15% by weight, the emission luminance of the obtained phosphor is greatly reduced. The amount of the binder used is about 0.01 to 1.0% by weight based on the phosphor. When the amount is less than 0.01% by weight, the adhesion between the phosphor and the pigment particles becomes insufficient, and when the amount is more than 1.0% by weight, the adhesion strength of the pigment becomes sufficient. And the dispersibility is poor, which is not preferable in practical use.
【００１５】次に、このスラリーを脱水し、乾燥して本
発明の青色顔料付蛍光体を得る。このようにして得られ
た本発明の青色顔料付蛍光体はその反射スペクトルを測
定した結果、平均粒子径が０．１μｍより大であるコバ
ルトブルー青色顔料が付着された従来の青色顔料付蛍光
体と比較して大差なく、熱や電子線に対する安定性を備
えている上、青色顔料の付着力が平均粒子径０．１μｍ
より大であるコバルトブルー青色顔料が付着された従来
の青色顔料付蛍光体に比べて顔料付着力が強く、このス
ラリーに強制的にストレスを掛け、剥離の程度を比べて
みると、ストレスによる剥離が非常に少なく、顔料の剥
離の程度が著しく低かった。なお、本発明において各顔
料付蛍光体の顔料剥離の程度の大小は下記の試験法によ
り行った。Next, the slurry is dehydrated and dried to obtain the phosphor with a blue pigment of the present invention. As a result of measuring the reflection spectrum of the thus obtained phosphor with a blue pigment of the present invention, a conventional phosphor with a blue pigment to which a cobalt blue blue pigment having an average particle diameter of more than 0.1 μm is attached. It has not much difference as compared to that of having stability against heat and electron beams, and has an adhesive force of a blue pigment having an average particle diameter of 0.1 μm.
Compared to the conventional phosphor with a blue pigment to which a larger cobalt blue pigment is attached, the pigment adhesion is stronger, and the slurry is forcibly stressed, and the degree of peeling is compared. Was very low, and the degree of peeling of the pigment was extremely low. In the present invention, the magnitude of the degree of pigment peeling of each pigmented phosphor was determined by the following test method.
【００１６】２０ｇの顔料付蛍光体を２００ｍｌの水中
に投入し、４００ｋＷの家庭用ミキサーに投入して１分
間攪拌して強制的にストレスを掛けてから、３００ｍｌ
の透明ガラス製のビーカーに移して１時間放置しておい
た後、その上澄み液を分取し、分光光度計を用いて６０
０ｎｍの単色光を照射して各上澄み液の光透過率を測定
してそれぞれを比較し、この時の光透過率が高い顔料付
蛍光体ほどその顔料剥離の程度が小さい蛍光体であると
認定した。20 g of the pigmented phosphor is put into 200 ml of water, put into a 400 kW household mixer, stirred for 1 minute, and forcibly stressed.
Was transferred to a transparent glass beaker and allowed to stand for 1 hour, and the supernatant was collected and subjected to a spectrophotometer for 60 minutes.
The light transmittance of each supernatant liquid was measured by irradiating a monochromatic light of 0 nm, and the light transmittance of each supernatant was measured and compared with each other. The phosphor with a higher light transmittance at this time was determined to be a phosphor with a smaller degree of pigment peeling. did.
【００１７】[0017]
【実施例】次に実施例により本発明を説明する。 〔実施例１〕コバルトブルー微粒子顔料（大日精化工業
株式会社製、＃３４８０、比重４．２）１７５重量部
と、ポリビニルアルコール（重合度５５０、ケン化度８
８）８．８重量部と、脱イオン水９９２重量部とガラス
ビーズ（直径３ｍｍ）１３００重量部とを混合し、これ
をガラス製ポットに入れて１１０回転で７時間かけてミ
リングを施して顔料を分散させ、実施例１のコバルトブ
ルー青色顔料の分散顔料スラリーを得た。この分散顔料
スラリーを分取して島津製作所製レーザー式粒度測定器
（型番；ＳＡ−ＣＰ３）でスラリー中の顔料粒子の粒度
を測定したところ、その平均粒径は０．０８μｍであっ
た。なお、この粒径の測定値はある一定以上の負荷を与
えてもそれ以上粒度がほとんど変化しない分散化条件と
して、容量の５０ｍｌの円錐型ビーカーに微量の分散剤
を含んだ脱イオン水３ｍｌと上記分散顔料スラリーを入
れ、これを超音波分散機（海上電機社製、ＡＵＴＯ Ｃ
ＨＡＳＥＲ ３００）によって出力２５Ｗで１分間分散
処理する条件を選定し、この分散処理条件で分散化した
試料中の顔料の粒度をレーザー式粒度測定器で測定した
値である。Next, the present invention will be described by way of examples. [Example 1] 175 parts by weight of cobalt blue fine particle pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., # 3480, specific gravity 4.2) and polyvinyl alcohol (degree of polymerization 550, degree of saponification 8)
8) 8.8 parts by weight, 992 parts by weight of deionized water, and 1300 parts by weight of glass beads (3 mm in diameter) are mixed, put into a glass pot, milled at 110 rotations for 7 hours, and pigment Was dispersed to obtain a dispersed pigment slurry of the cobalt blue blue pigment of Example 1. The dispersed pigment slurry was fractionated, and the particle size of the pigment particles in the slurry was measured by a laser type particle sizer (model number: SA-CP3) manufactured by Shimadzu Corporation. The average particle size was 0.08 μm. In addition, the measured value of the particle size is such that as a dispersing condition that the particle size hardly changes even when a certain load or more is applied, 3 ml of deionized water containing a small amount of a dispersing agent in a conical beaker having a capacity of 50 ml is used. The above-mentioned dispersed pigment slurry was put in, and this was used as an ultrasonic dispersing machine (manufactured by Marine Electronics, AUTO C).
HASER 300) is a value obtained by selecting the conditions for dispersion processing at an output of 25 W for 1 minute and measuring the particle size of the pigment in the sample dispersed under these dispersion processing conditions using a laser type particle size analyzer.
【００１８】一方、これとは別に 平均粒径７μｍの銀
付活硫化亜鉛青色発光蛍光体１００重量部に対し、５０
℃の脱イオン水１００重量部を加えてスラリー化し、こ
れに上記顔料スラリーを、顔料量として５重量部添加
し、さらに０．３重量部のゼラチンと０．３重量部のア
ラビアゴムを加温溶解した溶液を添加後、酢酸でｐＨ４
に調整した。更にゼラチン硬化剤として５０％のグルタ
ルアルデヒドを１ｍｌ加えて１５時間攪拌した後に濾過
し、１２０℃で乾燥し、篩い機を使用して４００メッシ
ュステインレス網で粉砕してコバルトブルー青色顔料を
付着させた実施例１の青色顔料付蛍光体を得た。On the other hand, separately from 100 parts by weight of a silver-activated zinc sulfide blue light-emitting phosphor having an average particle size of 7 μm,
100 parts by weight of deionized water at 0 ° C. are added to form a slurry. The pigment slurry is added in an amount of 5 parts by weight as a pigment, and 0.3 parts by weight of gelatin and 0.3 parts by weight of gum arabic are heated. After addition of the dissolved solution, the solution was adjusted to pH 4 with acetic acid.
Was adjusted. Further, 1 ml of 50% glutaraldehyde as a gelatin hardener was added, and the mixture was stirred for 15 hours, filtered, dried at 120 ° C., pulverized with a 400 mesh stainless net using a sieving machine, and allowed to adhere a cobalt blue blue pigment. The phosphor with the blue pigment of Example 1 was obtained.
【００１９】この青色顔料付蛍光体の顔料付着力を測る
ために、２０ｇの青色顔料付蛍光体を２００ｍｌの０．
１％水ガラス溶液の水中に投入し、４００ｋＷの家庭用
ミキサーに投入して１分間攪拌して強制的にストレスを
掛けてから、３００ｍｌの透明ガラス製のビーカーに移
して１時間放置しておいた後、その上澄み液を分取し、
これを１ｃｍ角の石英セルに入れて被測定試料液とし、
分光光度計によりこの被測定試料液に６００ｎｍの単色
光を照射してこの時の光透過率を測定した。なお、参照
試料として脱イオン水を用い、この脱イオン水（参照試
料）の透過率が１００％となるように光透過率測定系の
感度補正を行った。その結果、この被測定試料液の光透
過率は４５％であった。また、この青色顔料付蛍光体の
波長６００ｎｍにおける反射率は３０％であった。To measure the pigment adhesion of the blue pigmented phosphor, 20 g of the blue pigmented phosphor was added to 200 ml of 0. 0 ml.
Pour into 1% water glass solution water, pour into a 400 kW household mixer, stir for 1 minute to apply stress, then transfer to a 300 ml clear glass beaker and leave for 1 hour. After that, separate the supernatant liquid,
This is put into a 1 cm square quartz cell to be a sample liquid to be measured,
The sample liquid to be measured was irradiated with monochromatic light of 600 nm by a spectrophotometer, and the light transmittance at this time was measured. Note that deionized water was used as a reference sample, and the sensitivity of the light transmittance measurement system was corrected so that the transmittance of the deionized water (reference sample) was 100%. As a result, the light transmittance of the sample liquid to be measured was 45%. The reflectance of the phosphor with a blue pigment at a wavelength of 600 nm was 30%.
【００２０】〔比較例１〕青色顔料として、大日精化工
業株式会社製コバルトブルー顔料（＃３４８０）に代え
て、同じく大日精化工業株式会社製コバルトブルー顔料
（＃９４５３、顔料比重４．２）を用いた以外は実施例
１の分散顔料スラリーと同様にして比較例１の分散顔料
スラリーを調製した。この顔料の平均粒径は実施例１と
同様にして測定したところ、０．２５μｍであった。Comparative Example 1 As a blue pigment, instead of the cobalt blue pigment (# 3480) manufactured by Dainichi Seika Kogyo Co., Ltd., a cobalt blue pigment (# 9453, pigment specific gravity 4.2) also manufactured by Dainichi Seika Kogyo Co., Ltd. A dispersion pigment slurry of Comparative Example 1 was prepared in the same manner as in the dispersion pigment slurry of Example 1 except that the above-mentioned was used. The average particle size of this pigment was 0.25 μm as measured in the same manner as in Example 1.
【００２１】次いで、蛍光体に対して５重量％の顔料粒
子を含む上記比較例１の顔料スラリーを用いた以外は実
施例１と全く同様にして比較例１の青色顔料付蛍光体を
得た。この青色顔料付蛍光体の顔料付着力を測るため
に、実施例１と同様の操作を施して撹拌後の上澄み液試
料の６００ｎｍにおける光透過率を測定したところ上澄
み液の透過率は１５％であった。また、この青色顔料付
蛍光体の波長６００ｎｍにおける反射率は３２％であっ
た。Next, a phosphor with a blue pigment of Comparative Example 1 was obtained in exactly the same manner as in Example 1 except that the pigment slurry of Comparative Example 1 containing 5% by weight of pigment particles with respect to the phosphor was used. . In order to measure the pigment adhesion of this phosphor with a blue pigment, the same operation as in Example 1 was performed, and the light transmittance at 600 nm of the supernatant liquid sample after stirring was measured. The transmittance of the supernatant liquid was 15%. there were. The reflectance of the phosphor with a blue pigment at a wavelength of 600 nm was 32%.
【００２２】〔比較例２〕青色顔料として、大日精化工
業株式会社製コバルトブルー顔料（＃９４５３）に代え
てハーショーケミカル社製コバルトブルー顔料（＃９５
４６、顔料比重４．２）を用いた以外は実施例１の分散
顔料スラリーと同様にして比較例２の分散顔料スラリー
を調製した。このスラリー中の顔料の平均粒径は実施例
１と同様にして測定したところ、０．１４μｍであっ
た。Comparative Example 2 As a blue pigment, a cobalt blue pigment (# 95, manufactured by Harsha Chemical Co., Ltd.) was used in place of the cobalt blue pigment (# 9453, manufactured by Dainichi Seika Kogyo Co., Ltd.).
A dispersion pigment slurry of Comparative Example 2 was prepared in the same manner as the dispersion pigment slurry of Example 1 except that the pigment specific gravity was 4.2). The average particle size of the pigment in this slurry was 0.14 μm when measured in the same manner as in Example 1.
【００２３】次いで、蛍光体に対して５重量％の顔料粒
子を含む上記比較例２の顔料スラリーを用いた以外は実
施例１と全く同様にして比較例２の青色顔料付蛍光体を
得た。この青色顔料付蛍光体の顔料付着力を測るため
に、実施例１と同様の操作を施して撹拌後の上澄み液試
料の６００ｎｍにおける光透過率を測定したところ上澄
み液の透過率は２１％であった。また、この青色顔料付
蛍光体の波長６００ｎｍにおける反射率は３１％であっ
た。Next, a phosphor with a blue pigment of Comparative Example 2 was obtained in exactly the same manner as in Example 1 except that the pigment slurry of Comparative Example 2 containing 5% by weight of pigment particles with respect to the phosphor was used. . In order to measure the pigment adhesion of the phosphor with a blue pigment, the same operation as in Example 1 was performed to measure the light transmittance at 600 nm of the supernatant sample after stirring. As a result, the transmittance of the supernatant was 21%. there were. The reflectance of the phosphor with a blue pigment at a wavelength of 600 nm was 31%.
【００２４】実施例１、比較例１及び比較例２の結果か
らわかるように、蛍光体に対して同一量の顔料を付着し
た実施例１、比較例１及び比較例２の各顔料付蛍光体で
は、青色顔料付蛍光体の反射率特性の比較を行う上での
目安とされる波長６００ｎｍにおける反射率はほぼ同一
レベルにあるが、蛍光体に付着させる青色顔料の平均粒
径がおよそ０．１μｍより大である場合（比較例１及び
２）と、０．１μｍより小である場合（実施例１）とで
は、顔料剥離の程度が判断出来る試料上澄み液の光透過
率が大きく異なり、蛍光体に付着させる青色顔料の平均
粒径がほぼ０．１μｍより小であれば顔料付蛍光体のス
ラリーをミキサーにより攪拌し、これを一定時間静置し
た後のスラリー上澄み液の光透過率がかなり高く、顔料
剥離の著しい減少が認められる。このように本発明の青
色顔料付蛍光体は、少なくともバインダーの量が蛍光体
に対して１．０重量％よりも少ない場合、粒子径が０．
１μｍより大の青色顔料粒子を用いた以外はその組成が
同一である従来の青色顔料付蛍光体よりも顔料の剥離の
程度が小さい。As can be seen from the results of Example 1, Comparative Examples 1 and 2, each of the pigment-containing phosphors of Examples 1, Comparative Examples 1 and 2 having the same amount of pigment adhered to the phosphor. In this example, the reflectance at a wavelength of 600 nm, which is a standard for comparing the reflectance characteristics of the phosphors with blue pigments, is almost the same level, but the average particle size of the blue pigment attached to the phosphors is about 0.1. The light transmittance of the sample supernatant, from which the degree of pigment exfoliation can be determined, differs greatly between the case where the size is larger than 1 μm (Comparative Examples 1 and 2) and the case where the size is smaller than 0.1 μm (Example 1). If the average particle size of the blue pigment to be attached to the body is less than approximately 0.1 μm, the slurry of the phosphor with the pigment is stirred by a mixer, and after allowing the slurry to stand for a certain period of time, the light transmittance of the slurry supernatant is considerable. High, significant reduction in pigment peeling It is fit. As described above, the phosphor with a blue pigment of the present invention has a particle diameter of 0.1 at least when the amount of the binder is less than 1.0% by weight based on the phosphor.
Except for using blue pigment particles larger than 1 μm, the degree of peeling of the pigment is smaller than that of a conventional phosphor with a blue pigment having the same composition.
【００２５】[0025]
【発明の効果】本発明は上述のような構成としたので、
蛍光体に付着させる顔料を多くしても顔料の付着力が強
く、顔料剥離が少なくて高コントラストの青色顔料付蛍
光体となる。Since the present invention has the above-described configuration,
Even if the number of pigments to be adhered to the phosphor is increased, the adhesion of the pigment is strong, the pigment peeling is small, and a phosphor with a blue pigment of high contrast is obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岩崎 和人 神奈川県小田原市成田1060番地 化成オプ トニクス株式会社小田原工場内 Ｆターム(参考） 4H001 CA02 CA06 CC06 CC13 CC15 XA16 XA30 YA47 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuto Iwasaki 1060 Narita, Odawara-shi, Kanagawa F-term in Odawara Plant of Kasei Optonics Co., Ltd. 4H001 CA02 CA06 CC06 CC13 CC15 XA16 XA30 YA47
Claims (8)
０．１μｍ以下のコバルトブルーからなる青色顔料粒子
が付着していることを特徴とする青色顔料付蛍光体。1. A phosphor with a blue pigment, wherein blue pigment particles made of cobalt blue having an average particle diameter of 0.1 μm or less adhere to the surface of the blue light-emitting phosphor.
１〜０．１μｍであることを特徴とする請求項１に記載
の青色顔料付蛍光体。2. The blue pigment particles having an average particle size of 0.0
2. The phosphor with a blue pigment according to claim 1, wherein the thickness is 1 to 0.1 [mu] m.
前記青色発光蛍光体の表面に付着していることを特徴と
する請求項１ないし２に記載の青色顔料付蛍光体。3. The phosphor with a blue pigment according to claim 1, wherein the blue pigment particles are attached to a surface of the blue light emitting phosphor via a binder.
脂及びスチレンブタジエン樹脂の中の少なくとも１種で
あることを特徴とする請求項３に記載の青色顔料付蛍光
体。4. The phosphor with a blue pigment according to claim 3, wherein the binder is at least one of a natural resin, an acrylic resin, and a styrene-butadiene resin.
徴とする請求項４に記載の青色顔料付蛍光体。5. The phosphor with a blue pigment according to claim 4, wherein the natural resin is gelatin.
体に対して０．０１〜１．０重量％の範囲にあることを
特徴とする請求項３〜５に記載の青色顔料付蛍光体。6. The phosphor with a blue pigment according to claim 3, wherein the amount of the binder is in the range of 0.01 to 1.0% by weight based on the blue light emitting phosphor.
光蛍光体に対して０．３％〜１５重量％の範囲にあるこ
とを特徴とする請求項１〜６のいずれか１項に記載の青
色顔料付蛍光体。7. The blue light-emitting phosphor according to claim 1, wherein the adhesion amount of the blue pigment particles is in a range of 0.3% to 15% by weight based on the blue light-emitting phosphor. Phosphor with blue pigment.
対して１．０重量％以下のゼラチンを介してコバルトブ
ルー青色顔料粒子を付着させた青色顔料付蛍光体であっ
て、前記コバルトブルー青色顔料粒子の平均粒子径が
０．１μｍより大である以外は組成が同一である青色顔
料付蛍光体よりも前記コバルトブルー青色顔料の剥離の
程度が少ないことを特徴とする青色顔料付蛍光体。8. A phosphor with a blue pigment in which cobalt blue pigment particles are attached to the surface of a blue light-emitting phosphor via gelatin of 1.0% by weight or less with respect to the phosphor, A blue pigment-equipped fluorescent material, wherein the degree of peeling of the cobalt blue blue pigment is smaller than that of a blue pigment-equipped phosphor having the same composition except that the average particle diameter of the blue-blue pigment particles is larger than 0.1 μm. body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000370755A JP2002129157A (en) | 2000-10-30 | 2000-10-30 | Blue pigment-attaching fluorescent substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000370755A JP2002129157A (en) | 2000-10-30 | 2000-10-30 | Blue pigment-attaching fluorescent substance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002129157A true JP2002129157A (en) | 2002-05-09 |
Family
ID=18840583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000370755A Pending JP2002129157A (en) | 2000-10-30 | 2000-10-30 | Blue pigment-attaching fluorescent substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002129157A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009215385A (en) * | 2008-03-07 | 2009-09-24 | Toda Kogyo Corp | Blue pigment with infrared reflectivity, coating material using the same, and resin composition |
| US8961683B2 (en) | 2008-03-07 | 2015-02-24 | Toda Kogyo Corporation | Infrared reflecting blue pigment, infrared reflecting green pigment, paint and resin composition using the infrared reflecting blue pigment, and paint and resin composition using the infrared reflecting green pigment |
| JP2016058213A (en) * | 2014-09-09 | 2016-04-21 | ウシオ電機株式会社 | Fluorescent light source device |
| US10208900B2 (en) | 2014-09-09 | 2019-02-19 | Ushio Denki Kabushiki Kaisha | Fluorescence light source device with wavelength conversion member with particular ratio between light transmission percentage and light reflection percentage |
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| JPH05209173A (en) * | 1992-01-29 | 1993-08-20 | Kasei Optonix Co Ltd | Method for producing blue pigment and pigment-adhered luminous fluorescent material |
| JPH1143670A (en) * | 1997-07-25 | 1999-02-16 | Dainippon Printing Co Ltd | Colored phosphor particle, and composition for forming phosphor layer |
| JPH11209752A (en) * | 1998-01-20 | 1999-08-03 | Nec Kansai Ltd | Pigment-coated blue illuminating fluorescent substance and its production |
| JPH11246855A (en) * | 1998-03-05 | 1999-09-14 | Hitachi Ltd | Phosphor and production of the same and color cathode ray tube and production of the same |
| JP2000075475A (en) * | 1998-09-02 | 2000-03-14 | Dainippon Printing Co Ltd | Composition for formation of color phosphor pattern, production of plasma display back pate, plasma display back plate and plasma display |
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| JPS6164784A (en) * | 1984-09-07 | 1986-04-03 | Kasei Optonix Co Ltd | Production of pigment-coated fluorescent material |
| JPH05209173A (en) * | 1992-01-29 | 1993-08-20 | Kasei Optonix Co Ltd | Method for producing blue pigment and pigment-adhered luminous fluorescent material |
| JPH1143670A (en) * | 1997-07-25 | 1999-02-16 | Dainippon Printing Co Ltd | Colored phosphor particle, and composition for forming phosphor layer |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009215385A (en) * | 2008-03-07 | 2009-09-24 | Toda Kogyo Corp | Blue pigment with infrared reflectivity, coating material using the same, and resin composition |
| US8961683B2 (en) | 2008-03-07 | 2015-02-24 | Toda Kogyo Corporation | Infrared reflecting blue pigment, infrared reflecting green pigment, paint and resin composition using the infrared reflecting blue pigment, and paint and resin composition using the infrared reflecting green pigment |
| US9260583B2 (en) | 2008-03-07 | 2016-02-16 | Toda Kogyo Corporation | Infrared reflecting blue pigment, infrared reflecting green pigment, paint and resin composition using the infrared reflecting blue pigment, and paint and resin composition using the infrared reflecting green pigment |
| JP2016058213A (en) * | 2014-09-09 | 2016-04-21 | ウシオ電機株式会社 | Fluorescent light source device |
| US10208900B2 (en) | 2014-09-09 | 2019-02-19 | Ushio Denki Kabushiki Kaisha | Fluorescence light source device with wavelength conversion member with particular ratio between light transmission percentage and light reflection percentage |
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