JP2012177100A - Phosphor paste, and method of manufacturing member for display - Google Patents
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本発明は、蛍光体粉末が均一に分散された蛍光体ペースト、特にプラズマディスプレイパネル（以下ＰＤＰとする）に用いる蛍光体ペーストおよびそれを用いたディスプレイ用部材の製造方法に関するものである。 The present invention relates to a phosphor paste in which phosphor powder is uniformly dispersed, particularly a phosphor paste used for a plasma display panel (hereinafter referred to as PDP) and a method for producing a display member using the same.
ＰＤＰは、前面ガラス基板と背面ガラス基板との間に備えられた放電空間内で電極間にプラズマ放電を生じさせ、上記放電空間内に封入されたガスから発生した紫外線により放電空間内の蛍光体が発光することにより表示を行うものである。一般的に、ＰＤＰの背面板は基板上にアドレス電極、アドレス電極を覆う誘電体層、誘電体層上に隔壁を有し、蛍光体層は、隔壁で区切られたセル内、すなわちセル底部である誘電体層上と隔壁の側面に形成されており、ＰＤＰの高輝度化と輝度ムラ抑制のためには、セル底部の誘電体層上面および隔壁の側面に適切な厚みで蛍光体層が形成され、かつ、セル間の蛍光体厚みばらつきを一定以下に抑える必要がある。一般に蛍光体層は蛍光体粉末、バインダー樹脂および有機溶剤を含む蛍光体ペーストをセル内に塗布し、乾燥、焼成して設けられる。また、蛍光体ペーストをセル内に高精度かつ均一に塗布する方法として、吐出孔を有するノズルを用いて、吐出孔から蛍光体ペーストを連続的に吐出しつつ、ノズルと、基板を相対的に移動させてストライプ状に塗布する方法が知られている（特許文献1参照）。 The PDP generates a plasma discharge between electrodes in a discharge space provided between a front glass substrate and a back glass substrate, and phosphors in the discharge space by ultraviolet rays generated from the gas enclosed in the discharge space. Is displayed by emitting light. In general, the back plate of the PDP has an address electrode on the substrate, a dielectric layer covering the address electrode, and a barrier rib on the dielectric layer, and the phosphor layer is in a cell separated by the barrier rib, that is, at the cell bottom. It is formed on a certain dielectric layer and on the side walls of the barrier ribs. To increase the brightness of the PDP and suppress uneven brightness, a phosphor layer is formed with an appropriate thickness on the top surface of the dielectric layer and the side walls of the barrier ribs. In addition, it is necessary to keep the phosphor thickness variation between cells below a certain level. In general, the phosphor layer is provided by applying a phosphor paste containing phosphor powder, a binder resin and an organic solvent in a cell, and drying and firing. In addition, as a method of applying the phosphor paste in the cell with high accuracy and uniformity, a nozzle having discharge holes is used to continuously discharge the phosphor paste from the discharge holes, while the nozzle and the substrate are relatively There is known a method of moving and applying in stripes (see Patent Document 1).
このような方法で蛍光体層を形成する場合に、セル底部、隔壁の側面に適切な厚みで蛍光体層を形成し、かつ、セル間の蛍光体厚みばらつきを一定以下に抑えるためには、蛍光体ペーストにはセルの底部と隔壁の側面への付着性や、塗布性に関わる分散安定性、レオロジー特性等の最適化、これら特性を一定期間安定して維持することが要求される。
このような蛍光体ペーストとして、ペースト中の蛍光体粉末、バインダー樹脂の組成比率適正化による改善（特許文献２参照）や蛍光体ペーストのｐＨを弱塩基性側にして蛍光体粉末の分散性を向上することによる改善（特許文献３参照）といった方法が行われてきた。しかしながらこれらの蛍光体ペーストはＰＤＰへの塗布時、気泡を巻き込みながらセル内に蛍光体ペーストが充填されることがあったため、ＰＤＰを焼成後、セル内に均一に蛍光体粉末が充填されず、塗布抜けが発生する場合があり、高精度かつ高品位の表示特性を示すＰＤＰを歩留まり良く作製するにはペースト特性として不十分であった。
When forming a phosphor layer by such a method, in order to form a phosphor layer with an appropriate thickness on the cell bottom and side walls of the partition wall, and to suppress phosphor thickness variation between cells below a certain level, The phosphor paste is required to optimize adhesion to the bottom of the cell and the side walls of the partition, dispersion stability and rheological characteristics related to coating properties, and to maintain these characteristics stably for a certain period.
As such a phosphor paste, the phosphor powder in the paste is improved by optimizing the composition ratio of the binder resin (see Patent Document 2), and the phosphor paste is made dispersible by setting the pH of the phosphor paste to a weakly basic side. A method such as improvement by improvement (see Patent Document 3) has been performed. However, when these phosphor pastes are applied to the PDP, the cells may be filled with the phosphor paste while entraining bubbles, so that after firing the PDP, the phosphor powder is not uniformly filled in the cells. In some cases, coating omission may occur, and the paste characteristics are insufficient to produce a PDP exhibiting high-precision and high-quality display characteristics with a high yield.
本発明は、ＰＤＰへの塗布時にセル内に気泡を巻き込みにくく、塗布抜けのない蛍光体ペーストを提供することを目的とする。 It is an object of the present invention to provide a phosphor paste that is less likely to entrap bubbles in a cell during application to a PDP and that does not miss application.
前記課題の達成のため、本発明の蛍光体ペーストは、蛍光体粉末、バインダー樹脂および有機溶剤を含み、ペースト中の固形分の含有量が合計で５０〜７０質量％の範囲内、バインダー樹脂１００質量部に対する蛍光体粉末の含有量が３００〜８００質量部の範囲内であって、かつ前記有機溶剤がジヒドロターピニルアセテート、ターピニルメチルエーテル、トリエチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテルおよびジエチレングリコールブチルメチルエーテルから選ばれる有機溶剤Ａ、テルピネオールおよびベンジルアルコールを含み、ペースト中の前記有機溶剤Ａの含有量が３〜１５質量％の範囲内、テルピネオールの含有量が１〜４０質量％の範囲内、ベンジルアルコールの含有量が４〜４０質量％の範囲内のものである。 In order to achieve the above object, the phosphor paste of the present invention contains phosphor powder, a binder resin and an organic solvent, and the total solid content in the paste is in the range of 50 to 70% by mass. The content of the phosphor powder with respect to parts by mass is in the range of 300 to 800 parts by mass, and the organic solvent is dihydroterpinyl acetate, terpinyl methyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether and diethylene glycol butyl methyl. An organic solvent A selected from ether, terpineol and benzyl alcohol, the content of the organic solvent A in the paste is in the range of 3 to 15% by mass, the content of terpineol is in the range of 1 to 40% by mass, benzyl The alcohol content is 4 to 40% by mass囲内 is intended.
無機ガラス粉末とのぬれ性が良好で、塗布時にセル内で短時間に蛍光体ペーストがぬれ広がるため、気泡の巻き込みがなく塗布抜けのないＰＤＰを得ることができる。 Since the wettability with the inorganic glass powder is good and the phosphor paste wets and spreads within the cell in a short time during coating, a PDP free from entrainment of bubbles and free from coating failure can be obtained.
本発明の蛍光体ペーストは、蛍光体粉末、バインダー樹脂、および有機溶剤としてジヒドロターピニルアセテート、ターピニルメチルエーテル、トリエチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテルおよびジエチレングリコールブチルメチルエーテルから選ばれる有機溶剤Ａ、テルピネオールおよびベンジルアルコールを含む。 The phosphor paste of the present invention comprises phosphor powder, binder resin, and organic solvent A selected from dihydroterpinyl acetate, terpinyl methyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether and diethylene glycol butyl methyl ether as the organic solvent, Includes terpineol and benzyl alcohol.
本発明の蛍光体ペーストに用いられる蛍光体粉末は特に限定されないが、赤色発光の蛍光体粉末ではＹ２Ｏ３：Ｅｕ、ＹＶＯ４：Ｅｕ、（Ｙ，Ｇｄ）ＢＯ３：Ｅｕ、（Ｙ，Ｇｄ）（Ｐ，Ｖ）Ｏ4：Ｅｕ、などが挙げられる。緑色発光の蛍光体粉末では、Ｚｎ２ＳｉＯ４：Ｍｎ、（Ｙ，Ｇｄ）ＢＯ３：Tbなどが挙げられる。青色発光の蛍光体粉末ではＢａＭｇＡｌ１０Ｏ１７：Ｅｕ、ＢａＭｇＡｌ１４Ｏ２３：Ｅｕ、ＢａＭｇＡｌ１６Ｏ２７：Ｅｕ、ＢａＭｇ２Ａｌ１４Ｏ２４：Ｅｕ、などが挙げられる。また各色の粉末の電荷を揃えるため、表面を金属酸化物で被膜してもよい。蛍光体粉末の平均粒子径としては０．２〜５μｍのものが好ましく１〜３μｍのものがより好ましい。平均粒子径が５μｍより大きくなると、ペースト作製後に放置した際に蛍光体粉末が沈降しやすく塗布ムラになりやすい傾向にあり、また平均粒子径が０．２μｍより小さくなると比表面積が増大し、蛍光体粉末が凝集しやすくなるため、蛍光体層が不均一になったりノズルの吐出孔がつまる等の問題が発生しやすくなる傾向がある。粉末の配合量は蛍光体ペースト中に４０〜６０質量％が好ましく、４０〜５０質量％がより好ましい。蛍光体粉末の配合量が４０質量％より小さいと、所望の蛍光体層の膜厚を得るための蛍光体ペーストの塗布膜厚が大きくなり、膜厚ムラを生じやすい。一方、蛍光体粉末の配合量が６０質量％よりも大きいと、蛍光体ペースト中の蛍光体粉末が沈降しやすくなったり、ペーストの粘度変化が生じやすくなる傾向にある。 The phosphor powder used in the phosphor paste of the present invention is not particularly limited. However, in the case of a phosphor powder emitting red light, Y 2 O 3 : Eu, YVO 4 : Eu, (Y, Gd) BO 3 : Eu, (Y, Gd) (P, V) O 4 : Eu, and the like. Examples of green phosphor powder include Zn 2 SiO 4 : Mn, (Y, Gd) BO 3 : Tb, and the like. Examples of blue phosphor powder include BaMgAl 10 O 17 : Eu, BaMgAl 14 O 23 : Eu, BaMgAl 16 O 27 : Eu, BaMg 2 Al 14 O 24 : Eu, and the like. In addition, the surface may be coated with a metal oxide in order to align the charge of each color powder. The average particle diameter of the phosphor powder is preferably 0.2 to 5 μm, and more preferably 1 to 3 μm. When the average particle diameter is larger than 5 μm, the phosphor powder tends to settle and uneven coating tends to occur when left after the paste is produced. When the average particle diameter is smaller than 0.2 μm, the specific surface area increases, and the fluorescence increases. Since the body powder tends to aggregate, problems such as non-uniform phosphor layers and clogged nozzle discharge holes tend to occur. 40-60 mass% is preferable in a fluorescent substance paste, and, as for the compounding quantity of powder, 40-50 mass% is more preferable. When the blending amount of the phosphor powder is less than 40% by mass, the coating thickness of the phosphor paste for obtaining a desired phosphor layer thickness is increased, and film thickness unevenness is likely to occur. On the other hand, if the blending amount of the phosphor powder is larger than 60% by mass, the phosphor powder in the phosphor paste tends to settle or the viscosity of the paste tends to change.
本発明で用いるバインダー樹脂としては、蛍光体ペーストを塗布した段階では隔壁の側面やセル底部に適度な膜厚で付着するほどの粘度を有し、焼成時に酸化または分解または気化し、炭化物が無機物中に残存しないことが必要で、アクリル樹脂やエチルセルロースが挙げられる。特に、蛍光体粉末の分散性の点でエチルセルロースが好ましい。バインダー樹脂の配合量は蛍光体ペースト中に５〜２０質量％が好ましく５〜１５質量％がより好ましい。バインダー樹脂の配合量が小さい方が焼き飛び性が良好となるが、配合量が５質量％より小さいと蛍光体ペーストの粘度が低下しやすく、蛍光体粉末に対する分散安定化効果が不足したり、蛍光体ペースト塗布に適合する粘度特性が得られにくくなるという問題がある。また、２０質量％より大きいとペーストの粘度が高くなりすぎる傾向がある。 As the binder resin used in the present invention, at the stage where the phosphor paste is applied, the binder resin has a viscosity enough to adhere to the side wall of the partition wall or the cell bottom with an appropriate film thickness, and is oxidized, decomposed or vaporized during firing, and the carbide is an inorganic substance. It is necessary not to remain in it, and examples thereof include acrylic resin and ethyl cellulose. In particular, ethyl cellulose is preferable from the viewpoint of dispersibility of the phosphor powder. 5-20 mass% is preferable in a fluorescent substance paste, and, as for the compounding quantity of binder resin, 5-15 mass% is more preferable. The smaller the blending amount of the binder resin, the better the burn-off property, but when the blending amount is less than 5% by mass, the viscosity of the phosphor paste tends to decrease, the dispersion stabilizing effect on the phosphor powder is insufficient, There is a problem that it is difficult to obtain viscosity characteristics suitable for phosphor paste application. On the other hand, if it is larger than 20% by mass, the viscosity of the paste tends to be too high.
蛍光体ペーストの塗布性及び形成される蛍光体層の形状と深く関わるものとして、蛍光体粉末量とバインダー樹脂であるエチルセルロースの量の関係が重要であり、本発明に置いてはバインダー樹脂１００質量部に対して蛍光体粉末３００〜８００質量部であることが必要である。より好ましくは、バインダー樹脂１００質量部に対して蛍光体粉末４００〜６００質量部である。 The relationship between the amount of the phosphor powder and the amount of ethyl cellulose as the binder resin is important as it is deeply related to the applicability of the phosphor paste and the shape of the phosphor layer to be formed. In the present invention, 100 mass of the binder resin. It is necessary that the phosphor powder is 300 to 800 parts by mass with respect to the part. More preferably, it is 400-600 mass parts of phosphor powder with respect to 100 mass parts of binder resin.
隔壁の側面及び底面に蛍光体層を形成する際、側面部分への蛍光体層の付着を促すためにバインダー樹脂１００質量部に対して蛍光体粉末３００〜８００質量部を満足する必要がある。さらにバインダー樹脂１００質量部に対して蛍光体粉末４００〜６００質量部であると、蛍光体層の最適な形状を保ちつつ、有機溶剤等でのペースト粘度の調節幅が大きくなる。バインダー樹脂１００質量部に対し蛍光体粉末が８００質量部を超えると隔壁側面の蛍光体層が厚く、底面が薄くなるため目的とする輝度が達成されない。また３００質量部より小さい場合は底面が厚く、隔壁側面が薄くなるため高視野角での輝度の低下を招く。 When forming the phosphor layer on the side and bottom surfaces of the partition walls, it is necessary to satisfy 300 to 800 parts by mass of phosphor powder with respect to 100 parts by mass of the binder resin in order to promote the adhesion of the phosphor layer to the side part. Furthermore, when the amount of the phosphor powder is 400 to 600 parts by mass with respect to 100 parts by mass of the binder resin, the adjustment range of the paste viscosity with an organic solvent or the like is increased while maintaining the optimum shape of the phosphor layer. When the phosphor powder exceeds 800 parts by mass with respect to 100 parts by mass of the binder resin, the phosphor layer on the side face of the partition wall is thick and the bottom surface is thin, so that the intended luminance is not achieved. If it is smaller than 300 parts by mass, the bottom surface is thick and the side wall of the partition wall is thin, which causes a reduction in luminance at a high viewing angle.
さらに、蛍光体ペースト中の有機溶剤を除いた成分である固形分の含有量は５０〜７０質量％である必要がある。５０質量％未満ではバインダー樹脂と蛍光体粉末の比率から、蛍光体ペースト中に必要な蛍光体粉末比率を得ることができず、所望の蛍光体層膜厚を得るための蛍光体ペーストの塗布膜厚が大きくなり、膜厚ムラを生じ易い問題がある。また隔壁で区切られたセル内に塗布する場合、隔壁の高さより蛍光体ペーストの塗布膜厚を大きくする必要があり、隣接するセル内に蛍光体ペーストが流れ込むため、混色が生じやすくなる問題がある。７０質量％より大きい時ではペーストの粘度が高くなり、吐出孔を有するノズルを用いて塗布する場合、吐出性および塗布性が低下する傾向にある。また、蛍光体層膜厚が大きくなり、隔壁、誘電体層及び前面板から形成される放電空間が小さくなり、放電特性が悪化する傾向がある。 Furthermore, content of solid content which is a component except the organic solvent in fluorescent substance paste needs to be 50-70 mass%. If it is less than 50% by mass, it is impossible to obtain the phosphor powder ratio required in the phosphor paste from the ratio of the binder resin to the phosphor powder, and the phosphor paste coating film for obtaining the desired phosphor layer thickness. There is a problem that the thickness is increased and the film thickness is likely to be uneven. In addition, when the coating is applied to the cells separated by the barrier ribs, it is necessary to make the coating thickness of the phosphor paste larger than the height of the barrier ribs, and the phosphor paste flows into the adjacent cells, so that color mixing is likely to occur. is there. When the content is larger than 70% by mass, the viscosity of the paste increases, and when applied using a nozzle having an ejection hole, the ejection properties and applicability tend to decrease. In addition, the phosphor layer thickness increases, the discharge space formed by the barrier ribs, the dielectric layer, and the front plate decreases, and the discharge characteristics tend to deteriorate.
本発明では蛍光体ペーストの基板に対するぬれ性を改善し、塗布性を向上させるために、多数の検討を行った。蛍光体ペーストに導入するためにはバインダー樹脂の溶解性、粘度、引火点といった条件があり、これらを満たすことを前提に高精細な背面板に対して塗布した場合においても、気泡を巻き込みにくく、塗布抜けが発生しづらい有機溶剤の探索を行った。この結果に基づき、本発明では、ジヒドロターピニルアセテート、ターピニルメチルエーテル、トリエチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテルおよびジエチレングリコールブチルメチルエーテルから選ばれる有機溶剤Ａを含有成分として用いることが必須である。前述の有機溶剤Ａは、蛍光体粉末を十分に分散させ、誘電体層、隔壁を構成するガラスに対してぬれ性が良いことに起因し塗布性の向上効果が得られると推定した。しかしながら、バインダー樹脂の溶解性が低いこと、また低粘度溶剤であることから有機溶剤Ａのみからなる単一溶剤でのペースト化はできない。そこで本願発明者が鋭意検討を行った結果、有機溶剤Ａ、テルピネオール、ベンジルアルコールをある割合の混合溶媒とすることが、塗布性や蛍光体層の膜厚などを必要とする程度に保つために十分な量のバインダー樹脂を溶解すると共に、蛍光体ペーストの粘度を吐出孔を有するノズルからの吐出に適当な程度に保つ点で必要となることを見いだした。 In the present invention, in order to improve the wettability of the phosphor paste to the substrate and to improve the coating property, many studies have been made. In order to introduce into the phosphor paste, there are conditions such as the solubility, viscosity, and flash point of the binder resin, and even when applied to a high-definition back plate on the premise of satisfying these, it is difficult to entrap bubbles, We searched for organic solvents that were difficult to lose coating. Based on this result, in the present invention, it is essential to use, as a component, an organic solvent A selected from dihydroterpinyl acetate, terpinyl methyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol butyl methyl ether. It was presumed that the organic solvent A described above sufficiently dispersed the phosphor powder and had good wettability with respect to the glass constituting the dielectric layer and the barrier ribs, and thus improved coatability was obtained. However, since the binder resin has low solubility and is a low-viscosity solvent, it cannot be made into a paste with a single solvent consisting only of the organic solvent A. Therefore, as a result of intensive studies by the inventor of the present application, the organic solvent A, terpineol, and benzyl alcohol are used as a mixed solvent in a certain ratio in order to keep the coating property and the thickness of the phosphor layer to the required levels. It has been found that a sufficient amount of the binder resin is dissolved and the viscosity of the phosphor paste is required to maintain an appropriate level for ejection from a nozzle having ejection holes.
有機溶剤の配合量は蛍光体ペースト中に有機溶剤Ａが３〜１５質量％、テルピネオールが１〜４０質量％、ベンジルアルコールが４〜４０質量％である。配合量がこの範囲以外では、ペースト粘度の高低を制御するのが困難になる。ここで、有機溶剤Ａの配合量は、複数種類の有機溶媒Ａを使用する場合はその合計の配合量を指す。有機溶剤Ａの配合量が３質量％より小さい場合は、無機ガラス粉末に与えるぬれ性の効果が小さくなり、塗布時に気泡を巻き込む恐れがある。有機溶剤Ａの配合量が１５質量％より大きいとペースト粘度が低くなってしまう。テルピネオールの配合量が１質量％より小さい場合は、テルピネオールがバインダー樹脂に対する溶解性が高いため、バインダー樹脂の溶解性を下げてしまい、塗布性が低下する。テルピネオールの配合量が４０質量％より大きいと、テルピネオールが高粘度溶剤であるために、ペースト粘度が高くなり、塗布性が低下する。ベンジルアルコールの配合量が４質量％より小さい場合は、ベンジルアルコールが低粘度溶剤であるため、ペースト粘度が高くなり、塗布性が低下する。ベンジルアルコールの配合量が４０質量％より大きい場合は、ペースト粘度が小さくなりすぎることで塗布時に過剰に塗れ広がり、塗布ムラなどの不具合が生じる。 The compounding amount of the organic solvent is 3 to 15% by mass of the organic solvent A, 1 to 40% by mass of terpineol, and 4 to 40% by mass of benzyl alcohol in the phosphor paste. If the blending amount is outside this range, it becomes difficult to control the level of paste viscosity. Here, the blending amount of the organic solvent A indicates the total blending amount when a plurality of types of organic solvents A are used. When the blending amount of the organic solvent A is less than 3% by mass, the wettability effect imparted to the inorganic glass powder is reduced, and there is a possibility that bubbles may be involved during application. When the blending amount of the organic solvent A is larger than 15% by mass, the paste viscosity is lowered. When the blending amount of terpineol is less than 1% by mass, terpineol has high solubility in the binder resin, so that the solubility of the binder resin is lowered and the coating property is lowered. When the blending amount of terpineol is larger than 40% by mass, since terpineol is a high viscosity solvent, the paste viscosity becomes high and the coating property is lowered. When the blending amount of benzyl alcohol is less than 4% by mass, since benzyl alcohol is a low-viscosity solvent, the paste viscosity becomes high and the coating property is lowered. When the blending amount of benzyl alcohol is larger than 40% by mass, the paste viscosity becomes too small, so that it spreads excessively at the time of coating and causes problems such as coating unevenness.
有機溶剤の配合量は、蛍光体ペースト中に、３０〜５０質量％であることが好ましく、４０〜５０質量％がより好ましい。有機溶剤の配合量が３０質量％より小さいと蛍光体ペーストの粘度が高くなりすぎ、レベリング不良により塗布面の平滑性が不良となる傾向がある。一方、有機溶剤の配合量が５０質量％より大きいとペースト粘度が小さくなりすぎることで蛍光体粉末が沈降しやすくなる、乾燥に多大な時間とエネルギーを要する、等の問題を生じる。 It is preferable that the compounding quantity of the organic solvent is 30-50 mass% in a fluorescent substance paste, and 40-50 mass% is more preferable. If the blending amount of the organic solvent is less than 30% by mass, the viscosity of the phosphor paste becomes too high, and the smoothness of the coated surface tends to be poor due to poor leveling. On the other hand, when the blending amount of the organic solvent is larger than 50% by mass, the viscosity of the paste becomes too small, so that the phosphor powder is liable to settle, and much time and energy are required for drying.
本発明の蛍光体ペーストは各種成分を所定の組成となるように調合した後、３本ローラーやメディア分散機などの混練・分散手段によって均質に混合・分散して作製する。蛍光体ペーストの粘度は塗布方法によって最適値は異なるものの、吐出孔を有するノズルを用いて隔壁間に蛍光体ペーストを塗布する方式においては、５０，０００〜８０，０００ｍＰａ・ｓが好ましい。５０，０００ｍＰａ・ｓ未満では、吐出孔を有するノズルを用いて塗布する際、吐出前に吐出孔から蛍光体ペーストが染み出す恐れがあり、塗布困難になることがある。また８０，０００ｍＰａ・ｓより大きい場合は吐出孔からの吐出時の圧力が高くなり過ぎるなど、ペーストの取扱が困難になる。 The phosphor paste of the present invention is prepared by preparing various components so as to have a predetermined composition, and then uniformly mixing and dispersing them by a kneading / dispersing means such as a three-roller or a media dispersing machine. Although the optimum viscosity of the phosphor paste varies depending on the application method, it is preferably 50,000 to 80,000 mPa · s in a method in which the phosphor paste is applied between the partition walls using a nozzle having discharge holes. If it is less than 50,000 mPa · s, when applying using a nozzle having discharge holes, the phosphor paste may ooze out from the discharge holes before discharge, which may make application difficult. On the other hand, when the viscosity is larger than 80,000 mPa · s, it is difficult to handle the paste because the pressure at the time of discharge from the discharge hole becomes too high.
本発明は前記の蛍光体ペーストを用いて基板上に塗布する工程を含むディスプレイの製造方法にも関する。 The present invention also relates to a display manufacturing method including a step of applying the phosphor paste on a substrate.
本発明のディスプレイパネル用部材の製造方法は、基板上に誘電体層および隔壁を有するパターン化基板の誘電体層及び隔壁で囲まれた溝部に、上述の蛍光体ペーストをストライプ状に塗布し、焼成することを特徴とする。以下、本発明のディスプレイパネル用部材の製造方法の一例を挙げる。 In the method for manufacturing a display panel member of the present invention, the phosphor paste described above is applied in a stripe shape to the groove surrounded by the dielectric layer and the partition wall of the patterned substrate having the dielectric layer and the partition wall on the substrate, It is characterized by firing. Hereinafter, an example of the manufacturing method of the member for display panels of this invention is given.
基板上に、書き込み電極として、感光性銀ペーストとしてフォトリソグラフィー法により、ストライプ状電極を形成し、この基板に誘電体ペーストをスクリーン印刷法により塗布した後、５００〜６００℃で焼成して誘電体層を形成する。 A stripe-shaped electrode is formed on a substrate as a writing electrode by a photolithography method as a photosensitive silver paste, and a dielectric paste is applied to the substrate by a screen printing method, and then baked at 500 to 600 ° C. Form a layer.
さらに誘電体層上に感光性ガラスペーストを用いて、フォトリソグラフィー法でパターンを形成した後、５００〜６００℃で１０〜６０分間焼成し、ストライプ状の隔壁パターンを形成する。 Further, a photosensitive glass paste is used on the dielectric layer to form a pattern by a photolithography method, followed by baking at 500 to 600 ° C. for 10 to 60 minutes to form a stripe-like partition wall pattern.
このようにして形成された隔壁に、上記蛍光体ペーストパターンを形成する。蛍光体ペーストパターンの形成方法は、例えばスクリーン印刷法、吐出孔を有するノズルから蛍光体ペーストを吐出する方法、感光性レジストもしくは蛍光体ペーストに感光性としてフォトリソグラフィーにより形成する方法などが挙げられる。この中でも吐出孔を有するノズルから蛍光体ペーストを吐出する方法が簡便で、低コストのＰＤＰを得ることができるため好ましい。蛍光体ペーストパターンを形成後、乾燥、焼成して隔壁の側面及び底面に蛍光体層を形成する。蛍光体ペーストの乾燥は、脱溶媒や樹脂成分の硬化（不飽和二重結合成分の熱重合による熱架橋など）を目的として行い、温度、時間は溶媒の沸点や樹脂成分の硬化温度等に合わせて設定できるが、通常、温度８０℃〜２００℃、乾燥時間１０〜３０分の条件で行うことが好ましい。また、焼成はバインダー樹脂などの有機成分の除去を主な目的として行い、有機成分の揮散しやすさや焼成しやすさなどの有機成分の特性や蛍光体粉末の耐熱性など無機成分の特性に応じて行うことが好ましい。乾燥、焼成共に多段階の焼成プロファイルで実施しても良い。特に焼成温度を多段階とする場合、有機成分が蛍光体表面で焼き焦げ、蛍光体層の発光特性が変化するなどの問題を回避しやすくなる。乾燥後に冷却を挟まず、連続的に焼成を行うことも蛍光体層の膜厚均一性確保などの点で好ましい。 The phosphor paste pattern is formed on the barrier ribs thus formed. Examples of the method of forming the phosphor paste pattern include a screen printing method, a method of discharging the phosphor paste from a nozzle having discharge holes, and a method of forming the photosensitive resist or the phosphor paste by photolithography as photosensitivity. Among them, the method of discharging the phosphor paste from the nozzle having the discharge holes is preferable because it is simple and a low-cost PDP can be obtained. After forming the phosphor paste pattern, it is dried and fired to form a phosphor layer on the side and bottom surfaces of the partition walls. The phosphor paste is dried for the purpose of solvent removal and curing of the resin component (thermal crosslinking by thermal polymerization of unsaturated double bond components, etc.), and the temperature and time are adjusted to the boiling point of the solvent, the curing temperature of the resin component, etc. Usually, it is preferable to carry out under conditions of a temperature of 80 ° C. to 200 ° C. and a drying time of 10 to 30 minutes. Baking is performed mainly for the purpose of removing organic components such as binder resin, depending on the characteristics of organic components such as the ease of volatilization of organic components and the ease of firing, and the characteristics of inorganic components such as the heat resistance of phosphor powders. It is preferable to carry out. Both drying and firing may be performed with a multi-stage firing profile. In particular, when the firing temperature is multistage, it is easy to avoid problems such as organic components scorching on the phosphor surface and changes in the light emission characteristics of the phosphor layer. It is also preferable from the standpoint of ensuring the uniformity of the phosphor layer thickness, for example, to carry out continuous baking without cooling after drying.
次に本発明の実施例をあげて説明するが、本発明はかかる実施例のみに限定されるものではない。 Next, examples of the present invention will be described. However, the present invention is not limited to such examples.
以下の材料を用い、蛍光体ペーストを調製した。
（Ａ）蛍光体粉末
（Ａ−１）青色蛍光体粉末：ＢａＭｇＡｌ１０Ｏ１７：Ｅｕ
（Ａ−２）赤色蛍光体粉末：（Ｙ，Ｇｄ）ＢＯ３：Ｅｕ
（Ａ−３）緑色蛍光体粉末：Ｚｎ２ＳｉＯ４：Ｍｎ
（Ｂ）バインダー樹脂
エチルセルロース樹脂
（Ｃ）有機溶剤
有機溶剤Ａ（表１に記載のもの）
テルピネオール
ベンジルアルコール
蛍光体粉末、バインダー樹脂、有機溶剤を混合、更にセラミックス製の３本ローラーで混練し、蛍光体ペーストを得た。各蛍光体ペーストの各成分及び配合量を表１に示す。
（Ｅ）感光性銀ペースト
以下の組成のペーストを用いた。
銀粒子（平均粒子径１．５μｍ、比表面積０．８０ｍ２／ｇ）：１５０質量部
アクリル酸１０質量％、メチルメタクリレート５０質量％、グリセリンモノアクリレート４０質量％からなるアクリル系共重合体樹脂（酸価３０ｍｇＫＯＨ／ｇ、水酸基価４１０ｍｇＫＯＨ／ｇ、重量平均分子量１２０００）：１２質量部
トリメチロールプロパントリアクリレート：６質量部
２−ベンジル−ジメチルアミノ−１−（４−モノフォリノフェニル）−ブタノン−１：３質量部
γ−ブチロラクトン：１８質量部
（Ｆ）誘電体ペースト
以下の組成ペーストを用いた。
ガラス転移点４７５℃、軟化点５１５℃のビスマス系ガラス：４０質量部
エチルセルロース樹脂（エトキシ含有率５０％）：５質量部
テルピネオール：４０質量部
（Ｇ）感光性ガラスペースト
以下のガラスペーストを用いた。
ガラス転移点４９１℃、軟化点５２８℃のガラス粉末：２４質量部
ガラス転移点６５２℃のフィラー粉末：６質量部
アクリル酸１０質量％、メチルメタクリレート５０質量％、グリセリンモノアクリレート４０質量％からなるアクリル系共重合体樹脂（酸価３０ｍｇＫＯＨ／ｇ、水酸基価４１０ｍｇＫＯＨ／ｇ、重量平均分子量１２０００）：７質量部
トリメチロールプロパントリアクリレート：３質量部
２−ベンジル−ジメチルアミノ−１−（４−モノフォリノフェニル）−ブタノン−１：１．５質量部
ウレタン化合物ＵＡ−３３４８ＰＥ：（新中村化学製）１．５質量部
次に以下の測定方法で実施例１〜１１及び比較例１〜７における粘度測定、蛍光体ペーストの塗布性の評価を行った。
１．粘度評価
以下の条件でペースト作製直後の粘度測定を行った。
A phosphor paste was prepared using the following materials.
(A) Phosphor powder (A-1) Blue phosphor powder: BaMgAl 10 O 17 : Eu
(A-2) Red phosphor powder: (Y, Gd) BO 3 : Eu
(A-3) Green phosphor powder: Zn 2 SiO 4 : Mn
(B) Binder resin Ethyl cellulose resin (C) Organic solvent Organic solvent A (listed in Table 1)
Terpineol benzyl alcohol phosphor powder, binder resin, and organic solvent were mixed and kneaded with three ceramic rollers to obtain a phosphor paste. Table 1 shows each component and blending amount of each phosphor paste.
(E) Photosensitive silver paste A paste having the following composition was used.
Silver particles (average particle size 1.5 μm, specific surface area 0.80 m 2 / g): acrylic copolymer resin (150 parts by mass of acrylic acid 10% by mass, methyl methacrylate 50% by mass, glycerin monoacrylate 40% by mass) Acid value 30 mgKOH / g, hydroxyl value 410 mgKOH / g, weight average molecular weight 12000): 12 parts by mass trimethylolpropane triacrylate: 6 parts by mass 2-benzyl-dimethylamino-1- (4-monoforinophenyl) -butanone- 1: 3 parts by mass γ-butyrolactone: 18 parts by mass (F) Dielectric paste The following composition paste was used.
Bismuth glass having a glass transition point of 475 ° C. and a softening point of 515 ° C .: 40 parts by mass ethyl cellulose resin (ethoxy content 50%): 5 parts by mass Terpineol: 40 parts by mass (G) The following glass paste was used. .
Glass powder having a glass transition point of 491 ° C and a softening point of 528 ° C: 24 parts by mass Filler powder having a glass transition point of 652 ° C: 6 parts by mass Acrylic acid 10% by mass, methyl methacrylate 50% by mass, glycerin monoacrylate 40% by mass Copolymer resin (acid value 30 mgKOH / g, hydroxyl value 410 mgKOH / g, weight average molecular weight 12000): 7 parts by mass trimethylolpropane triacrylate: 3 parts by mass 2-benzyl-dimethylamino-1- (4-monofori Nophenyl) -butanone-1: 1.5 parts by mass Urethane compound UA-3348PE: (manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.5 parts by mass Next, the viscosity in Examples 1-11 and Comparative Examples 1-7 by the following measurement method Measurement and applicability of the phosphor paste were evaluated.
1. Viscosity evaluation Viscosity measurement immediately after paste preparation was performed under the following conditions.
粘度測定において粘度計はＢ型粘度計（ブルックフィールド製、モデルＤＶ−II＋Ｐｒｏ）を用い、スピンドルはＳＣ４−１４、容器はスモールアダプター（サンプルカップ３ｃｃ）、測定温度は２５℃、ずり速度は１．２［ｓ−１］で測定を開始してから粘度値を読みとるまでの時間を５分とした。蛍光体ペーストの粘度は５０，０００〜８０，０００ｍＰａ・ｓの範囲を○とし、それ以外の範囲を×と評価した。
２．塗布性評価
以下に示す方法で背面板を作製した。
In the viscosity measurement, a B-type viscometer (Brookfield model DV-II + Pro) was used as the viscometer, the spindle was SC4-14, the container was a small adapter (sample cup 3 cc), the measurement temperature was 25 ° C., and the shear rate was 1. The time from the start of measurement at 2 [s −1 ] to reading of the viscosity value was 5 minutes. The viscosity of the phosphor paste was evaluated as ◯ in the range of 50,000 to 80,000 mPa · s, and x in the other ranges.
2. Evaluation of applicability A back plate was prepared by the following method.
次に、３４０×２６０×２．８ｍｍサイズのガラス基板（ＰＤ−２００；旭硝子（株）製）を使用してＡＣ（交流）型プラズマディスプレイパネルの背面板を形成した。基板上に書き込み電極として、感光性銀ペースト（Ｅ）を用いてフォトリソグラフィー法により、ピッチ１４０μｍ、線幅６０μｍ、焼成後厚み４μｍのストライプ状電極を形成した。この基板に誘電体ペースト（Ｆ）をスクリーン印刷法により塗布した後、５５０℃で焼成して、厚み１０μｍの誘電体層を形成した。 Next, a back plate of an AC (alternating current) type plasma display panel was formed using a glass substrate (PD-200; manufactured by Asahi Glass Co., Ltd.) having a size of 340 × 260 × 2.8 mm. A stripe-shaped electrode having a pitch of 140 μm, a line width of 60 μm, and a thickness of 4 μm after firing was formed on the substrate as a writing electrode by photolithography using a photosensitive silver paste (E). A dielectric paste (F) was applied to the substrate by a screen printing method and then baked at 550 ° C. to form a dielectric layer having a thickness of 10 μm.
さらに、誘電体層上に感光性ガラスペースト（Ｇ）を用いてフォトリソグラフィー法でパターン形成後、５７０℃で１５分間焼成し、ピッチ１４０μｍ、線幅２０μｍ、高さ１００μｍのストライプ状の隔壁パターンを形成した。このようにして形成された隔壁パターン間に、表１に示した組成の蛍光体ペーストをピッチ４２０μｍ、孔径８０μｍ、孔長３００μｍの吐出孔を有するノズルを用いて塗布、１８０℃で１５分乾燥させた後、焼成（５００℃、３０分）して隔壁の側面および底部に蛍光体層を形成し、蛍光体層のセル内の蛍光体層の塗布抜けの有無を確認した。セル内の蛍光体層の塗布抜けが存在すると、そのセルは不灯セルとなり表示欠点となる。従来の評価方法は面内から任意の点を選び評価する方法であったが、本評価では背面板内の５０×５０ｍｍサイズ内を観察し、塗布抜けが無い場合を○、ある場合を×と評価した。 Further, a pattern is formed by photolithography using a photosensitive glass paste (G) on the dielectric layer, followed by baking at 570 ° C. for 15 minutes to form a stripe-shaped partition wall pattern having a pitch of 140 μm, a line width of 20 μm, and a height of 100 μm. Formed. The phosphor paste having the composition shown in Table 1 was applied between the barrier rib patterns thus formed using a nozzle having a discharge hole with a pitch of 420 μm, a hole diameter of 80 μm, and a hole length of 300 μm, and dried at 180 ° C. for 15 minutes. After that, firing (500 ° C., 30 minutes) was carried out to form a phosphor layer on the side and bottom of the partition wall, and it was confirmed whether or not the phosphor layer in the phosphor layer was coated. If there is a coating failure of the phosphor layer in the cell, the cell becomes a non-lighted cell, which causes a display defect. The conventional evaluation method was an evaluation method by selecting an arbitrary point from the in-plane, but in this evaluation, the inside of the back plate was observed within the 50 × 50 mm size, ○ when there was no coating omission, and x when there was evaluated.
表１に粘度測定及び塗布性評価の結果を示す。本発明の範囲内である蛍光体ペーストを用いた実施例１〜１９は塗布性が優れていたが、本発明の範囲外である蛍光体ペーストを用いた比較例１〜７では塗布性に劣る結果となった。 Table 1 shows the results of viscosity measurement and applicability evaluation. Examples 1 to 19 using phosphor pastes within the scope of the present invention were excellent in applicability, but Comparative Examples 1 to 7 using phosphor pastes outside the scope of the present invention were inferior in applicability. As a result.
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| WO2018225782A1 (en) * | 2017-06-08 | 2018-12-13 | 株式会社Ｄｎｐファインケミカル | Curable composition containing quantum dots, cured material containing quantum dots, method for manufacturing optical member, and method for manufacturing display device |
| WO2019069698A1 (en) * | 2017-10-04 | 2019-04-11 | Dic株式会社 | Ink and light-emitting element |
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| JPWO2018225782A1 (en) * | 2017-06-08 | 2020-04-09 | 株式会社Ｄｎｐファインケミカル | Quantum dot-containing curable composition, quantum dot-containing cured product, method for producing optical member, and method for producing display device |
| JP7216642B2 (en) | 2017-06-08 | 2023-02-01 | 株式会社Ｄｎｐファインケミカル | Quantum dot-containing curable composition, quantum dot-containing cured product, method for producing optical member, and method for producing display device |
| WO2019069698A1 (en) * | 2017-10-04 | 2019-04-11 | Dic株式会社 | Ink and light-emitting element |
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