JP4100591B2 - Lead-free glass powder and plasma display panel barrier rib composition - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、特にプラズマディスプレイパネル（以下ＰＤＰという。）の背面ガラス基板上の隔壁形成に好適な無鉛ガラス粉末およびＰＤＰ隔壁形成用組成物に関する。
【０００２】
【従来の技術】
従来からの陰極線管に代わるディスプレイとして、大型で薄型のＰＤＰが開発されてきている。
図１はＰＤＰの概略構成図である。ＰＤＰは２枚のガラス基板、すなわち前面ガラス基板１および背面ガラス基板２の内表面に、互いに直交するストライプ状の電極が配置される。前面ガラス基板１には表示電極３およびバス電極４が、背面ガラス基板２にはアドレス電極８が、それぞれ配置される。
【０００３】
各電極は誘電体膜５で被覆される。前面ガラス基板１の誘電体膜５は保護膜６で被覆される。背面ガラス基板２には高さ約１００μｍの隔壁７がアドレス電極８と同方向（縦方向）に配置され、隔壁７の間に蛍光体９の層が形成される。前面ガラス基板１および背面ガラス基板２の周辺を封止材（図示せず。）で気密封止した後Ｎｅ−Ｘｅ混合ガス等のガスが封入される。
【０００４】
隔壁７の形成方法として種々のものが提案されているが、近年の主流はサンドブラスト法と呼ばれる方法である。サンドブラスト法とは、ガラス基板表面に所定厚さの隔壁形成用組成物であるガラスペーストを塗布し、乾燥後、その上に耐ブラスト性を有する感光性ドライフィルムを重ね合わせ、次いで所定の隔壁形状に露光・現像を行ってパターニングした後、研磨粉を吹きつけて感光性ドライフィルムのない部分を削りとり、その後焼成を行って隔壁を形成する方法である。この方法を用いると高精細パターンの隔壁を形成できる。
【０００５】
サンドブラスト法で使用されるガラスペーストは、ガラスを主成分とし、無機顔料、無機充填材、等を含有する。前記ガラスは、ＰＤＰを構成するガラス基板上に前記方法で焼成されるため、ガラス基板として従来使用されているソーダライムシリカ系ガラス等の基板ガラスの耐熱性を考慮すると６００℃以下で焼成する必要がある。このため比較的低融点のガラスが用いられている。現在主流となっているガラスペーストのガラスは、ＰｂＯを５０重量％以上含有するＰｂＯ−ＳｉＯ2 系のガラスである。
【０００６】
以上述べたように、鉛含有低融点ガラスを主成分とするガラスペーストを用いてサンドブラスト法により隔壁を形成する方法が主流となっているが、サンドブラスト法では不必要な部分が削りとられるため、大量の鉛含有廃棄物が発生し、環境面で問題が発生するおそれがある。このためＰＤＰ隔壁形成用ガラスペーストとして無鉛のものが求められている。
【０００７】
【発明が解決しようとする課題】
本発明は、環境面で問題を発生させるおそれがある鉛を含有しない無鉛ガラス粉末およびＰＤＰ隔壁形成用組成物の提供を目的とする。
【０００８】
【課題を解決するための手段】
本発明は、酸化物基準のモル％表示で実質的に、ＺｎＯ：２５〜５５％、Ａｌ2 Ｏ3 ：１〜９％、Ｐ2 Ｏ5 ：３０〜５５％、ＳｉＯ2 ：０〜１５％、ＢａＯ＋ＣａＯ＋ＭｇＯ＋ＳｒＯ：０〜２０％、からなり、軟化点が４６０〜５９０℃で、最大粒子径が２〜２０μｍであるプラズマディスプレイパネル隔壁形成用無鉛ガラス粉末、および、前記無鉛ガラス粉末を含有するＰＤＰ隔壁形成用組成物、を提供する。
【０００９】
本発明者は、環境面で問題を発生させるおそれのないＺｎＯ、Ａｌ2 Ｏ3 、Ｐ2 Ｏ5 、等の酸化物に着目して鋭意研究を行った結果、鉛含有ガラスと同等の特性を有する安定な無鉛ガラス組成を見出し本発明に至った。
【００１０】
【発明の実施の形態】
本発明の無鉛ガラス粉末は、実質的に鉛を含有しないガラス粉末である。ＺｎＯは必須成分であり、５５モル％を超えると結晶化しやすくなり安定したガラスを得にくくなる。好ましくは４８モル％以下である。２５モル％未満では軟化点が高くなりすぎ所定温度での焼成が困難となる。好ましくは３０モル％以上である。
【００１１】
Ａｌ2Ｏ3は必須成分であり、耐水性を向上させる効果がある。１５モル％を超えると軟化点が高くなりすぎ所定温度での焼成が困難となる。好ましくは９モル％以下である。１モル％未満では耐水性を向上させる効果がなくなる。好ましくは２モル％以上である。
【００１２】
Ｐ2 Ｏ5 は必須成分であり、ガラスを形成する最も重要な成分である。５５モル％を超えると結晶化しやすくなり安定したガラスを得にくくなる。好ましくは５０モル％以下である。３０モル％未満では軟化点が高くなりすぎ所定温度での焼成が困難となる。好ましくは３８モル％以上である。
【００１３】
ＳｉＯ2 は必須成分ではないがガラスの安定化に効果があり、１５モル％まで含有してもよい。１５モル％を超えると軟化点が高くなりすぎ所定温度での焼成が困難となる。好ましくは１０モル％以下である。
【００１４】
アルカリ土類金属酸化物であるＢａＯ、ＣａＯ、ＭａＯ、ＳｒＯは、必須成分ではないが主として軟化点および熱膨張係数を調整するために有効な成分である。一般的なガラスと同様に、ＺｎＯ−Ａｌ2 Ｏ3 −Ｐ2 Ｏ5 の３成分ガラス系でも軟化点と熱膨張係数との間には相関があり、軟化点の上昇とともに熱膨張係数は減少する。このため、軟化点が同じであり熱膨張係数が違うガラスが必要な場合、または熱膨張係数が同じであり軟化点が違うガラスが必要な場合、ＺｎＯ−Ａｌ2 Ｏ3 −Ｐ2 Ｏ5 の３成分ガラス系ではその実現はきわめて困難である。しかし、これらアルカリ土類金属酸化物の含有量を調整することにより、軟化点が同じであり熱膨張係数が違うガラス、または熱膨張係数が同じであり軟化点が違うガラスを作製できる。
【００１５】
熱膨張係数を増加させる効果は、ＢａＯ＞ＳｒＯ＞ＣａＯ＞ＭｇＯの順に小さくなる。また、軟化点を上昇させる効果は、ＭｇＯ＞ＣａＯ＞ＳｒＯ＞ＢａＯの順に小さくなる。
ＢａＯ、ＣａＯ、ＭａＯ、ＳｒＯは、それらの合量が２０モル％まで含有してもよい。２０モル％を超えると結晶化しやすくなり安定したガラスを得にくくなる。好ましくは１２モル％以下である。
【００１６】
上記成分以外に、Ｆｅ2 Ｏ3 のような着色成分を０．５モル％まで添加してもよい。また、その他の成分を本発明の目的を損なわない範囲で添加してもよいがその合量は５モル％以下である。
【００１７】
本発明の無鉛ガラス粉末の軟化点は４６０〜５９０℃である。５９０℃を超えると、ＰＤＰ隔壁形成工程においてガラス基板上に、本発明の無鉛ガラス粉末を含有するＰＤＰ隔壁形成用組成物を６００℃以下で焼成する場合、前記ＰＤＰ隔壁形成用組成物の流動性が低下し高精細パターンの隔壁形成が困難となり、またガラス基板との接着性も低下する。
【００１８】
軟化点が４６０℃未満では、ＰＤＰ製造工程の最後に行われる前面ガラス基板と背面ガラス基板の周辺の気密封止に際して問題が発生する。すなわち、前記気密封止においては４５０℃程度の熱処理が行われるが、軟化点が４６０℃未満では隔壁形状が変形して、隔壁下部が広がり隔壁間の幅が狭くなる、隔壁の高さも低くなり所定の幅・高さ比が得られなくなる、等の問題が発生する。
【００１９】
本発明の無鉛ガラス粉末の「３０〜３００℃における平均線膨張係数」（以下、熱膨張係数という。）は５０×１０-7〜９５×１０-7／℃であることが好ましい。理由を以下に述べる。
【００２０】
背面ガラス基板としては熱膨張係数が７０×１０-7〜８５×１０-7／℃であるソーダライムシリカ系ガラス等が一般的に用いられるが、背面ガラス基板上に形成される隔壁はＰＤＰ製造工程において熱処理を数回受けるためその熱膨張係数と背面ガラス基板の熱膨張係数との差は小さいことが望ましい。その差は好ましくは１０×１０-7／℃以下であり、隔壁の熱膨張係数は６０×１０-7〜８５×１０-7／℃であることが好ましい。
【００２１】
本発明のＰＤＰ隔壁形成用組成物は本発明の無鉛ガラス粉末の他に、隔壁の熱膨張係数調整のために無機充填材または無機顔料を含有することが好ましい。本発明の無鉛ガラス粉末の熱膨張係数が５０×１０-7〜９５×１０-7／℃であれば、前記熱膨張係数調整により隔壁の熱膨張係数を前記好ましい範囲である６０×１０-7〜８５×１０-7／℃とすることができる。
【００２２】
本発明の無鉛ガラス粉末の熱膨張係数が９５×１０-7／℃を超えると隔壁の膨張係数が８５×１０-7／℃を超え、隔壁にクラックが入ったり、はがれたりするおそれがある。５０×１０-7／℃未満では隔壁の膨張係数が６０×１０-7／℃未満となり、背面ガラス基板にクラックが入ったり、背面ガラス基板が変形したりするおそれがある。
【００２３】
本発明のＰＤＰ隔壁形成用組成物は、本発明の無鉛ガラス粉末を含有する。本発明のＰＤＰ隔壁形成用組成物は、上記無鉛ガラス粉末に加え、無機充填剤および／または無機顔料を含有することが好ましい。
【００２４】
無機充填材は隔壁の熱膨張係数調整の他に、隔壁の強度向上、焼成時の収縮率調整または隔壁の緻密性調整のために使用される。隔壁の強度向上のためには、アルミナ、ジルコニア、等が使用される。隔壁の熱膨張係数調整のためには、ジルコン、コージエライト、ムライト、非晶質シリカ、アルミナ、フォルステライト、α−石英、蛍石、等が使用される。
【００２５】
無機顔料は隔壁の熱膨張係数調整の他に、隔壁の着色、焼成時の収縮率調整または隔壁の緻密性調整のために使用される。隔壁の色調を白色にするためには、酸化チタン、アルミナ、等が使用される。隔壁の色調を黒色にするためには、Ｃｕ−Ｃｒ系、Ｃｕ−Ｃｒ−Ｍｎ系、等が使用される。
【００２６】
熱膨張係数調整、等のために無機充填材または無機顔料を過剰に添加すると、所定温度での焼成に際し、ＰＤＰ隔壁形成用組成物の流動性が低下して高精細パターンの隔壁形成が困難となり、またガラス基板との接着性も低下するおそれがある。
【００２７】
無機充填材および無機顔料の合量は無鉛ガラス粉末１００重量部に対して５〜２００重量部が好ましい。５重量部未満の場合、焼成時の収縮率は大きくなりすぎるおそれがある。より好ましくは１０重量部以上、特に好ましくは１５重量部以上である。２００重量部超の場合、隔壁の緻密性が低下するおそれがある。より好ましくは１００重量部以下、特に好ましくは４５重量部以下である。
【００２８】
本発明のＰＤＰ隔壁形成用組成物は、バインダおよび有機溶媒を含有することが好ましい。無鉛ガラス、無機充填材、無機顔料、等の粉末はバインダおよび有機溶媒と混合してガラスペーストとされ、印刷等により背面ガラス基板に塗布後、焼成、パターニングされＰＤＰの隔壁となる。
【００２９】
バインダおよび有機溶媒は、特に限定されることなく、従来使用されているものを使用できる。
バインダとしては、たとえば、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシエチル・エチルセルロースのようなセルロース系材料、ポリビニルブチラール、ポリビニルアセテート、ポリビニルアルコール、等が用いられる。有機溶媒としては、たとえば、α−テルピネオール、ブチルカルビトールアセテート、２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート、等が用いられる。
【００３０】
無鉛ガラス、無機充填材、無機顔料、等の粉末の最大粒子径は２〜２０μｍであることが好ましい。２０μｍ超では、焼成後の隔壁を緻密化し、高精細パターンの隔壁を得ることが困難になるおそれがある。好ましくは１５μｍ以下である。２μｍ未満ではガラスペーストの粘度が高くなりすぎ作業性が損なわれるおそれがある。
【００３１】
本発明のＰＤＰ隔壁形成用組成物は、従来のガラスペーストと同様な方法で製造される。すなわち、所定の組成となるように原料を調合、混合し、加熱溶融した後、金型に流し込み無鉛ガラスのブロックを得る。次いでボールミル等の粉砕機で粉砕し、無鉛ガラス粉末を作製する。所望する特性が得られるように無鉛ガラス粉末に無機充填材、無機顔料を配合・混合後、バインダおよび有機溶媒を加え３本ロールミル等で混練しガラスペーストとする。
【００３２】
【実施例】
次に実施例を示して本発明を具体的に説明するが、本発明は下記実施例に限定されない。
表１に示す組成（単位：モル％）となるように、各原料を調合し、白金ルツボに入れ、１２００〜１４００℃の電気炉中で、２時間加熱して溶融させた後、急冷して板状に成形し、板状のガラスブロックを得た。次いで、このガラスブロックをボールミルを用いて粉砕して最大粒子径２〜２０μｍのガラス粉末を得た。これらのガラスについてガラス転移点、軟化点および熱膨張係数を測定し、また得られたガラス粉末の最大粒子径を測定した。測定法を以下に記すとともに、測定結果を表１に示す。
【００３３】
ガラス転移点（℃）および軟化点（℃）：ガラスを粉末とし、示差熱分析装置を用いて測定した。昇温速度は１０℃／ｍｉｎとした。
熱膨張係数（×１０-7／℃）：示差膨張計により３０〜３００℃における平均線膨張係数を測定した。昇温速度は１０℃／ｍｉｎとした。
最大粒子径（μｍ）：レーザ回折式粒度分布測定機により測定した。
【００３４】
表１において、例１〜６は実施例、例７〜８は比較例である。例１〜６は安定したガラスが得られた。これに対して例７はガラスとならず、また例８はガラス化したが軟化点が高く、熱膨張係数も大きいものとなった。
【００３５】
例１〜６および例８のガラス粉末に、表２に示す無機充填材および無機顔料を、表２の含有量（単位：重量％）の欄に示す割合で混合した。さらにバインダとしてエチルセルロース、溶剤としてα−テルピネオールを添加し、よく撹拌した後、セラミック製３本ロールミルを用いて混練し、粘度が１５×１０4 センチポアズのガラスペーストを作製した。
【００３６】
次いで、熱膨張係数が８３×１０-7／℃であるソーダライムシリカガラスの基板にスクリーン印刷でガラスペーストを印刷し、１２５℃で１０分間乾燥した後、５６０℃で３０分間焼成し、高さ１００μｍの焼成体を形成した。このガラス基板上に形成された焼成体を光学顕微鏡で観察し、クラック、はがれの有無を調べた。結果を表２の評価の欄に示した。
【００３７】
例１〜６のガラス、各種無機充填材および各種無機顔料とを組み合わせて得られた焼成体にはクラック、はがれが認められず、ＰＤＰ隔壁として適したものである。これに対して、例８のガラスを使用した焼成体にはクラック、はがれが認められ、ＰＤＰ隔壁としては適さないものであった。
【００３８】
【表１】
【表２】
【発明の効果】
本発明の無鉛ガラス粉末およびＰＤＰ隔壁形成用組成物は鉛成分を含有せず、環境面での問題を発生させるおそれがない。また、背面ガラス基板または隔壁におけるクラック、背面ガラス基板からの隔壁のはがれ、が起りにくいＰＤＰ隔壁を形成できる。
【図面の簡単な説明】
【図１】ＰＤＰの概略構成図。
【符号の説明】
１：前面ガラス基板
２：背面ガラス基板
３：表示電極
４：パス電極
５：誘電体膜
６：保護膜
７：隔壁
８：アドレス電極
９：蛍光体[0001]
BACKGROUND OF THE INVENTION
The present invention particularly relates to a lead-free glass powder and a composition for forming PDP barrier ribs suitable for forming barrier ribs on a back glass substrate of a plasma display panel (hereinafter referred to as PDP).
[0002]
[Prior art]
Large and thin PDPs have been developed as displays to replace conventional cathode ray tubes.
FIG. 1 is a schematic configuration diagram of a PDP. In the PDP, striped electrodes orthogonal to each other are arranged on the inner surfaces of two glass substrates, that is, the front glass substrate 1 and the rear glass substrate 2. Display electrodes 3 and bus electrodes 4 are arranged on the front glass substrate 1, and address electrodes 8 are arranged on the rear glass substrate 2.
[0003]
Each electrode is covered with a dielectric film 5. The dielectric film 5 of the front glass substrate 1 is covered with a protective film 6. On the rear glass substrate 2, partition walls 7 having a height of about 100 μm are arranged in the same direction (longitudinal direction) as the address electrodes 8, and a phosphor 9 layer is formed between the partition walls 7. After the front glass substrate 1 and the back glass substrate 2 are hermetically sealed with a sealing material (not shown), a gas such as a Ne—Xe mixed gas is sealed.
[0004]
Various methods for forming the partition walls 7 have been proposed, but the mainstream in recent years is a method called a sand blast method. Sand blasting is a method of applying a glass paste, which is a partition wall forming composition having a predetermined thickness on the surface of a glass substrate, drying, overlaying a photosensitive dry film having blast resistance thereon, and then forming a predetermined partition wall shape. Then, after patterning by exposure / development, polishing powder is sprayed to scrape off the portion without the photosensitive dry film, followed by firing to form partition walls. When this method is used, partition walls having a high definition pattern can be formed.
[0005]
The glass paste used in the sandblasting method contains glass as a main component and contains an inorganic pigment, an inorganic filler, and the like. Since the glass is fired on the glass substrate constituting the PDP by the above method, it is necessary to fire at 600 ° C. or lower in consideration of the heat resistance of the substrate glass such as soda lime silica glass conventionally used as the glass substrate. There is. For this reason, a glass having a relatively low melting point is used. The glass paste glass that is currently mainstream is a PbO—SiO 2 glass containing 50% by weight or more of PbO.
[0006]
As described above, the method of forming the partition wall by the sand blast method using a glass paste mainly composed of lead-containing low-melting glass has become mainstream, but unnecessary portions are scraped off by the sand blast method. A large amount of lead-containing waste is generated, which may cause environmental problems. For this reason, a lead-free glass paste for forming a PDP barrier rib is required.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a lead- free glass powder containing no lead and a composition for forming a PDP barrier rib, which may cause environmental problems.
[0008]
[Means for Solving the Problems]
The present invention is substantially represented by mol% based on oxides, ZnO: 25~55%, Al 2 O 3: 1~ 9%, P 2 O 5: 30~55%, SiO 2: 0~15% , BaO + CaO + MgO + SrO: 0 to 20%, lead-free glass powder for forming a plasma display panel partition having a softening point of 460 to 590 ° C. and a maximum particle size of 2 to 20 μm , and a PDP partition containing the lead-free glass powder A forming composition is provided.
[0009]
As a result of earnest research focusing on oxides such as ZnO, Al 2 O 3 , P 2 O 5 , etc., which have no risk of causing environmental problems, the present inventors have obtained characteristics equivalent to lead-containing glass. The present inventors have found a stable lead-free glass composition having the present invention.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Pb-free glass powder of the present invention is a glass powder contains substantially no lead. ZnO is an essential component, and if it exceeds 55 mol%, it becomes easy to crystallize and it becomes difficult to obtain a stable glass. Preferably it is 48 mol% or less. If it is less than 25 mol%, the softening point becomes too high, and firing at a predetermined temperature becomes difficult. Preferably it is 30 mol% or more.
[0011]
Al 2 O 3 is an essential component and has an effect of improving water resistance. If it exceeds 15 mol%, the softening point becomes too high and firing at a predetermined temperature becomes difficult. Preferably it is 9 mol% or less. If it is less than 1 mol%, the effect of improving water resistance is lost. Preferably it is 2 mol% or more.
[0012]
P 2 O 5 is an essential component and is the most important component for forming glass. When it exceeds 55 mol%, it becomes easy to crystallize and it becomes difficult to obtain a stable glass. Preferably it is 50 mol% or less. If it is less than 30 mol%, the softening point becomes too high, and firing at a predetermined temperature becomes difficult. Preferably it is 38 mol% or more.
[0013]
Although SiO 2 is not an essential component, it is effective for stabilizing the glass and may be contained up to 15 mol%. If it exceeds 15 mol%, the softening point becomes too high and firing at a predetermined temperature becomes difficult. Preferably it is 10 mol% or less.
[0014]
BaO, CaO, MaO, and SrO, which are alkaline earth metal oxides, are not essential components but are effective components mainly for adjusting the softening point and the thermal expansion coefficient. Similar to general glass, the ZnO—Al 2 O 3 —P 2 O 5 ternary glass system has a correlation between the softening point and the thermal expansion coefficient, and the thermal expansion coefficient decreases as the softening point increases. To do. For this reason, when glasses having the same softening point and different thermal expansion coefficients are required, or when glasses having the same thermal expansion coefficient and different softening points are required, ZnO—Al 2 O 3 —P 2 O 5 Realization is very difficult in a three-component glass system. However, by adjusting the content of these alkaline earth metal oxides, glasses having the same softening point and different thermal expansion coefficients, or glasses having the same thermal expansion coefficient and different softening points can be produced.
[0015]
The effect of increasing the thermal expansion coefficient decreases in the order of BaO>SrO>CaO> MgO. Further, the effect of increasing the softening point decreases in the order of MgO>CaO>SrO> BaO.
BaO, CaO, MaO and SrO may contain up to 20 mol% of the total amount thereof. When it exceeds 20 mol%, it becomes easy to crystallize and it becomes difficult to obtain a stable glass. Preferably it is 12 mol% or less.
[0016]
In addition to the above components, a coloring component such as Fe 2 O 3 may be added up to 0.5 mol%. Further, other components may be added within a range not impairing the object of the present invention, but the total amount is 5 mol% or less.
[0017]
The softening point of the lead-free glass powder of the present invention is 460 to 590 ° C. When the temperature exceeds 590 ° C., when the PDP barrier rib forming composition containing the lead-free glass powder of the present invention is baked at 600 ° C. or lower on the glass substrate in the PDP barrier rib forming step, the fluidity of the PDP barrier rib forming composition As a result, the formation of high-definition pattern partition walls becomes difficult, and the adhesion to the glass substrate also decreases.
[0018]
If the softening point is less than 460 ° C., a problem occurs when the periphery of the front glass substrate and the back glass substrate is hermetically sealed at the end of the PDP manufacturing process. That is, in the hermetic sealing, a heat treatment of about 450 ° C. is performed, but when the softening point is less than 460 ° C., the shape of the partition is deformed, the lower portion of the partition is widened, and the width between the partitions is narrowed. There arises a problem that a predetermined width / height ratio cannot be obtained.
[0019]
The “average linear expansion coefficient at 30 to 300 ° C.” (hereinafter referred to as thermal expansion coefficient) of the lead-free glass powder of the present invention is preferably 50 × 10 −7 to 95 × 10 −7 / ° C. The reason is described below.
[0020]
As the back glass substrate, soda lime silica glass having a thermal expansion coefficient of 70 × 10 −7 to 85 × 10 −7 / ° C. is generally used, but the partition formed on the back glass substrate is manufactured by PDP. Since the heat treatment is performed several times in the process, it is desirable that the difference between the thermal expansion coefficient and the thermal expansion coefficient of the rear glass substrate is small. The difference is preferably 10 × 10 −7 / ° C. or less, and the thermal expansion coefficient of the partition walls is preferably 60 × 10 −7 to 85 × 10 −7 / ° C.
[0021]
In addition to the lead-free glass powder of the present invention, the PDP partition wall forming composition of the present invention preferably contains an inorganic filler or an inorganic pigment for adjusting the thermal expansion coefficient of the partition wall. When the thermal expansion coefficient of the lead-free glass powder of the present invention is 50 × 10 −7 to 95 × 10 −7 / ° C., the thermal expansion coefficient of the partition wall is 60 × 10 −7, which is the preferred range, by adjusting the thermal expansion coefficient. It can be set to ˜85 × 10 −7 / ° C.
[0022]
If the thermal expansion coefficient of the lead-free glass powder of the present invention exceeds 95 × 10 −7 / ° C., the expansion coefficient of the partition wall exceeds 85 × 10 −7 / ° C., and the partition wall may be cracked or peeled off. If it is less than 50 × 10 −7 / ° C., the expansion coefficient of the partition walls is less than 60 × 10 −7 / ° C., which may cause cracks in the back glass substrate or deformation of the back glass substrate.
[0023]
The composition for forming a PDP barrier rib of the present invention contains the lead-free glass powder of the present invention. The composition for forming a PDP barrier rib of the present invention preferably contains an inorganic filler and / or an inorganic pigment in addition to the lead-free glass powder .
[0024]
In addition to adjusting the thermal expansion coefficient of the partition wall, the inorganic filler is used for improving the strength of the partition wall, adjusting the shrinkage ratio during firing, or adjusting the density of the partition wall. In order to improve the strength of the partition walls, alumina, zirconia, or the like is used. For adjusting the thermal expansion coefficient of the partition walls, zircon, cordierite, mullite, amorphous silica, alumina, forsterite, α-quartz, fluorite, and the like are used.
[0025]
In addition to adjusting the thermal expansion coefficient of the partition wall, the inorganic pigment is used for coloring the partition wall, adjusting the shrinkage during firing, or adjusting the density of the partition wall. In order to make the color of the partition wall white, titanium oxide, alumina, or the like is used. In order to make the color tone of the partition wall black, Cu-Cr, Cu-Cr-Mn, or the like is used.
[0026]
If an excessive amount of inorganic filler or inorganic pigment is added to adjust the thermal expansion coefficient, etc., the flowability of the composition for forming the PDP barrier ribs decreases during firing at a predetermined temperature, making it difficult to form barrier ribs with high definition patterns. In addition, the adhesiveness with the glass substrate may be lowered.
[0027]
The total amount of the inorganic filler and the inorganic pigment is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the lead-free glass powder . If the amount is less than 5 parts by weight, the shrinkage rate during firing may be too large. More preferably, it is 10 parts by weight or more, and particularly preferably 15 parts by weight or more. If it exceeds 200 parts by weight, the denseness of the partition walls may be reduced. More preferably, it is 100 parts by weight or less, and particularly preferably 45 parts by weight or less.
[0028]
The composition for forming a PDP barrier rib of the present invention preferably contains a binder and an organic solvent. Powders such as lead-free glass, inorganic filler, and inorganic pigment are mixed with a binder and an organic solvent to form a glass paste. After being applied to the back glass substrate by printing or the like, it is fired and patterned to form PDP partition walls.
[0029]
The binder and the organic solvent are not particularly limited, and those conventionally used can be used.
As the binder, for example, cellulose materials such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxyethyl / ethyl cellulose, polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, and the like are used. As the organic solvent, for example, α-terpineol, butyl carbitol acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and the like are used.
[0030]
The maximum particle size of powders such as lead-free glass, inorganic fillers, and inorganic pigments is preferably 2 to 20 μm. If it exceeds 20 μm, it may be difficult to obtain a high-definition pattern partition by densifying the partition after firing. Preferably it is 15 micrometers or less. If it is less than 2 μm, the viscosity of the glass paste becomes too high, and workability may be impaired.
[0031]
The composition for forming a PDP barrier rib of the present invention is produced by a method similar to that for a conventional glass paste. That is, the raw materials are prepared and mixed so as to have a predetermined composition, heated and melted, and then poured into a mold to obtain a lead-free glass block. Subsequently, it grind | pulverizes with grinders, such as a ball mill, and produces lead-free glass powder. A lead-free glass powder is blended and mixed with an inorganic filler and an inorganic pigment so as to obtain desired characteristics, and then a binder and an organic solvent are added and kneaded with a three-roll mill or the like to obtain a glass paste.
[0032]
【Example】
EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.
Each raw material was prepared so as to have the composition shown in Table 1 (unit: mol%), put in a platinum crucible, heated and melted in an electric furnace at 1200 to 1400 ° C. for 2 hours, and then rapidly cooled. It shape | molded in plate shape and obtained the plate-shaped glass block. Next, the glass block was pulverized using a ball mill to obtain a glass powder having a maximum particle size of 2 to 20 μm. The glass transition point, softening point, and thermal expansion coefficient of these glasses were measured, and the maximum particle size of the obtained glass powder was measured. The measurement method is described below, and the measurement results are shown in Table 1.
[0033]
Glass transition point (° C.) and softening point (° C.): Glass was powdered and measured using a differential thermal analyzer. The heating rate was 10 ° C./min.
Thermal expansion coefficient (× 10 −7 / ° C.): The average linear expansion coefficient at 30 to 300 ° C. was measured with a differential dilatometer. The heating rate was 10 ° C./min.
Maximum particle size (μm): Measured with a laser diffraction particle size distribution analyzer.
[0034]
In Table 1, Examples 1 to 6 are Examples, and Examples 7 to 8 are Comparative Examples. In Examples 1 to 6 , stable glass was obtained. In contrast, Example 7 was not glass, and Example 8 was vitrified but had a high softening point and a large thermal expansion coefficient.
[0035]
Inorganic powders and inorganic pigments shown in Table 2 were mixed with the glass powders of Examples 1 to 6 and Example 8 in the proportions shown in the column of content (unit: weight%) shown in Table 2. Further, ethyl cellulose as a binder and α-terpineol as a solvent were added and stirred well, and then kneaded using a ceramic three-roll mill to prepare a glass paste having a viscosity of 15 × 10 4 centipoise.
[0036]
Next, a glass paste was printed by screen printing on a soda lime silica glass substrate having a thermal expansion coefficient of 83 × 10 −7 / ° C., dried at 125 ° C. for 10 minutes, and then baked at 560 ° C. for 30 minutes. A 100 μm fired body was formed. The fired body formed on the glass substrate was observed with an optical microscope to examine the presence or absence of cracks and peeling. The results are shown in the evaluation column of Table 2.
[0037]
In the fired bodies obtained by combining the glasses of Examples 1 to 6 , various inorganic fillers, and various inorganic pigments, cracks and peeling are not observed, and they are suitable as PDP partition walls. On the other hand, cracks and peeling were observed in the fired body using the glass of Example 8 , which was not suitable as a PDP partition wall.
[0038]
[Table 1]
[Table 2]
【The invention's effect】
The lead-free glass powder and the composition for forming a PDP barrier rib of the present invention do not contain a lead component, and there is no risk of causing environmental problems. In addition, it is possible to form a PDP partition wall in which cracks in the rear glass substrate or the partition walls and separation of the partition walls from the rear glass substrate hardly occur.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram of a PDP.
[Explanation of symbols]
1: Front glass substrate 2: Rear glass substrate 3: Display electrode 4: Pass electrode 5: Dielectric film 6: Protective film 7: Partition wall 8: Address electrode 9: Phosphor
Claims (5)
０〜１５％、ＢａＯ＋ＣａＯ＋ＭｇＯ＋ＳｒＯ ０〜２０％、からなり、軟化点が４６０〜５９０℃で、最大粒子径が２〜２０μｍであるプラズマディスプレイパネル隔壁形成用無鉛ガラス粉末。Substantially expressed in terms of mol% based on oxide, ZnO 25-55%, Al 2 O 3 1-9%, P 2 O 5 30-55%, SiO 2
A lead-free glass powder for forming a plasma display panel barrier rib, comprising 0-15%, BaO + CaO + MgO + SrO 0-20%, having a softening point of 460-590 ° C. and a maximum particle size of 2-20 μm.
０〜１０％、ＢａＯ＋ＣａＯ＋ＭｇＯ＋ＳｒＯ ０〜１２％、からなる請求項１記載のプラズマディスプレイパネル隔壁形成用無鉛ガラス粉末。Substantially expressed in terms of mol% based on oxide, ZnO 30 to 48%, Al 2 O 3 2 to 9%, P 2 O 5 38 to 50%, SiO 2
The lead-free glass powder for forming a plasma display panel barrier rib according to claim 1, comprising 0 to 10%, BaO + CaO + MgO + SrO 0 to 12%.
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| JP22321098A JP4100591B2 (en) | 1998-08-06 | 1998-08-06 | Lead-free glass powder and plasma display panel barrier rib composition |
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| JP22321098A JP4100591B2 (en) | 1998-08-06 | 1998-08-06 | Lead-free glass powder and plasma display panel barrier rib composition |
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| JP4100591B2 true JP4100591B2 (en) | 2008-06-11 |
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| JP4597336B2 (en) * | 1999-09-22 | 2010-12-15 | 日本山村硝子株式会社 | Magnesium phosphate glass composition |
| WO2004110956A1 (en) * | 2003-06-11 | 2004-12-23 | Mitsubishi Materials Corporation | Lead-free glass composition and pdp barrier rib using the same |
| JP2005022961A (en) * | 2003-06-11 | 2005-01-27 | Mitsubishi Materials Corp | Glass composition, mixture, paste, green sheet and plasma display panel |
| JP2005022962A (en) * | 2003-06-11 | 2005-01-27 | Mitsubishi Materials Corp | Glass composition, mixture, paste, green sheet and plasma display panel |
| JP2005063835A (en) * | 2003-08-13 | 2005-03-10 | Fujitsu Hitachi Plasma Display Ltd | Glass composition for plasma display panel formation and plasma display panel using it |
| JP4394036B2 (en) * | 2004-09-09 | 2010-01-06 | 豊田合成株式会社 | Solid state device |
| JP2006137665A (en) * | 2004-10-14 | 2006-06-01 | Mitsubishi Materials Corp | Coating composition, mixture, paste and electronic component |
| JP2006137666A (en) * | 2004-10-14 | 2006-06-01 | Mitsubishi Materials Corp | Glass composition, mixture, paste and electronic component |
| KR20070118915A (en) | 2006-06-13 | 2007-12-18 | 엘지전자 주식회사 | Driving method for plasma display panel |
| EP2163531A1 (en) * | 2008-09-11 | 2010-03-17 | Samsung SDI Co., Ltd. | Material for forming barrier ribs and pdp comprising the same |
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