JP4239238B2 - Glass paste composition for forming glass sintered body and transfer film - Google Patents

Description

【００２１】
〔式中、Ｒ¹ は水素原子またはメチル基を示し、Ｒ² は１価の有機基を示す。〕
【００２２】
上記一般式（１）で表される（メタ）アクリレート化合物の具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレートなどのアルキル（メタ）アクリレート；
ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、３−ヒドロキシブチル（メタ）アクリレートなどのヒドロキシアルキル（メタ）アクリレート；
フェノキシエチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレートなどのフェノキシアルキル（メタ）アクリレート；
２−メトキシエチル（メタ）アクリレート、２−エトキシエチル（メタ）アクリレート、２−プロポキシエチル（メタ）アクリレート、２−ブトキシエチル（メタ）アクリレート、２−メトキシブチル（メタ）アクリレートなどのアルコキシアルキル（メタ）アクリレート；
ポリエチレングリコールモノ（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、エトキシポリプロピレングリコール（メタ）アクリレート、ノニルフェノキシポリプロピレングリコール（メタ）アクリレートなどのポリアルキレングリコール（メタ）アクリレート；
シクロヘキシル（メタ）アクリレート、４−ブチルシクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタジエニル（メタ）アクリレート、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレートなどのシクロアルキル（メタ）アクリレート；
ベンジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレートなどを挙げることができる。
これらのうち、上記一般式（１）中、Ｒ² で示される基が、アルキル基またはオキシアルキレン基を含有する基であることが好ましく、特に好ましい（メタ）アクリレート化合物として、メチル（メタ）アクリレート、ブチル（メタ）アクリレート、エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソデシル（メタ）アクリレートおよび２−エトキシエチル（メタ）アクリレートを挙げることができる。
（メタ）アクリレート化合物との共重合に供される他の共重合性単量体としては、上記（メタ）アクリレート化合物と共重合可能な化合物であれば特に制限はなく、例えば（メタ）アクリル酸、ビニル安息香酸、マレイン酸、ビニルフタル酸などの不飽和カルボン酸類；ビニルベンジルメチルエーテル、ビニルグリシジルエーテル、スチレン、α−メチルスチレン、ブタジエン、イソプレンなどのビニル基含有ラジカル重合性化合物を挙げることができる。本発明の組成物を構成するアクリル樹脂において、上記一般式（１）で表される（メタ）アクリレート化合物由来の共重合成分は、通常７０重量％以上、好ましくは９０重量％以上、さらに好ましくは１００重量％である。
本発明の組成物を構成する結着樹脂の分子量としては、ＧＰＣによるポリスチレン換算の重量平均分子量として２，０００〜３００，０００であることが好ましく、さらに好ましくは５，０００〜２００，０００とされる。
【００２３】
本発明の組成物における結着樹脂の含有割合としては、ガラス粉末１００重量部に対して、５〜４０重量部であることが好ましく、さらに好ましくは１０〜３０重量部とされる。結着樹脂の割合が過小である場合には、ガラス粉末を確実に結着保持することができず、一方、この割合が過大である場合には、焼成工程に長い時間を要したり、形成されるガラス焼結体（誘電体層）が十分な強度や膜厚を有するものとならなかったりする。
【００２４】
＜溶剤＞
本発明の組成物を構成する溶剤としては、ガラス粉末との親和性、結着樹脂の溶解性が良好で、ガラスペースト組成物に適度な粘性を付与することができると共に、乾燥されることにより容易に蒸発除去できるものであることが好ましい。
また、特に好ましい溶剤として、標準沸点（１気圧における沸点）が１００〜２００℃であるケトン類、アルコール類およびエステル類（以下、これらを「特定溶剤」という。）を挙げることができる。
かかる特定溶剤の具体例としては、ジエチルケトン、メチルブチルケトン、ジプロピルケトン、シクロヘキサノンなどのケトン類；ｎ−ペンタノール、４−メチル−２−ペンタノール、シクロヘキサノール、ジアセトンアルコールなどのアルコール類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテルなどのエーテル系アルコール類；酢酸−ｎ−ブチル、酢酸アミルなどの飽和脂肪族モノカルボン酸アルキルエステル類；乳酸エチル、乳酸−ｎ−ブチルなどの乳酸エステル類；メチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、エチル−３−エトキシプロピオネートなどのエーテル系エステル類などを例示することができ、これらのうち、メチルブチルケトン、シクロヘキサノン、ジアセトンアルコール、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、乳酸エチル、エチル−３−エトキシプロピオネートなどが好ましい。これらの特定溶剤は、単独でまたは２種以上を組み合わせて使用することができる。
特定溶剤以外の溶剤の具体例としては、テレビン油、エチルセロソルブ、メチルセロソルブ、テルピネオール、ブチルカルビトールアセテート、ブチルカルビトール、イソプロピルアルコール、ベンジルアルコールなどを挙げることができる。
本発明の組成物における溶剤の含有割合としては、組成物の粘度を好適な範囲に維持する観点から、ガラス粉末１００重量部に対して、５〜５０重量部であることが好ましく、さらに好ましくは１０〜４０重量部とされる。
また、全溶剤に対する特定溶剤の含有割合は、５０重量％以上であることが好ましく、更に好ましくは７０重量％以上とされる。
【００２５】
本発明のガラス焼結体形成用ガラスペースト組成物には、上記の必須成分のほかに、分散剤、粘着性付与剤、可塑剤、表面張力調整剤、安定剤、消泡剤、分散剤などの各種添加剤が任意成分として含有されていてもよい。
好ましいガラスペースト組成物の一例を示せば、酸化鉛５０〜８０重量％、酸化ホウ素５〜２０重量％、酸化ケイ素１０〜２５重量％、酸化カルシウム０〜５重量％からなる混合物からなり、平均粒子径が２μｍ、粒子径が１０μｍ以上である粒子の割合が１重量％、粒子径が０．７〜２．５μｍの範囲にある粒子の割合が９０重量％、ＢＥＴ比表面積が２．５ｍ² ／ｇ、Ｂｌａｉｎ値が１０，０００であるガラス粉末１００重量部と、ポリブチルメタクリレート（アクリル樹脂）１０〜３０重量部と、プロピレングリコールモノメチルエーテル（溶剤）１０〜５０重量部とを必須成分として含有する組成物を挙げることができる。
本発明の組成物は、上記ガラス粉末、結着樹脂および溶剤並びに任意成分を、ロール混練機、ミキサー、ホモミキサー、サンドミルなどの混練・分散機を用いて混練することにより調製することができる。
上記のようにして調製される本発明の組成物は、塗布に適した流動性を有するペースト状の組成物である。
【００２６】
本発明の組成物は、転写フィルムを製造するために特に好適に使用することができる。この転写フィルムは、支持フィルムと、この支持フィルム上に形成された膜形成材料層とにより構成され、ドライフィルム法による誘電体層の形成工程に使用される複合材料である。ここに、ドライフィルム法による支持フィルムへの塗布工程に供されるガラスペースト組成物（本発明の組成物）の粘度としては、１，０００〜３０，０００であることが好ましい。
転写フィルムを構成する支持フィルムは、耐熱性及び耐溶剤性を有するとともに可撓性を有する樹脂フィルムであることが好ましい。支持フィルムが可撓性を有することにより、ロールコーター、ブレードコーターなどによって本発明の組成物を塗布することができ、膜形成材料層をロール状に巻回した状態で保存し、供給することができる。支持フィルムを形成する樹脂としては、例えばポリエチレンテレフタレート、ポリエステル、ポリエチレン、ポリプロピレン、ポリスチレン、ポリイミド、ポリビニルアルコール、ポリ塩化ビニル、ポリフロロエチレンなどの含フッ素樹脂、ナイロン、セルロースなどを挙げることができる。支持フィルムの厚さとしては、例えば２０〜１００μｍとされる。
転写フィルムを構成する膜形成材料層は、本発明の組成物を前記支持フィルム上に塗布し、塗膜を乾燥して溶剤の一部又は全部を除去することにより形成することができる。
本発明の組成物を支持フィルム上に塗布する方法としては、膜厚の均一性に優れた膜厚の大きい（例えば２０μｍ以上）塗膜を効率よく形成することができるものであることが好ましく、具体的には、ロールコーターによる塗布方法、ブレードコーターによる塗布方法、カーテンコーターによる塗布方法、ワイヤーコーターによる塗布方法などを好ましいものとして挙げることができる。
なお、本発明の組成物が塗布される支持フィルムの表面には離型処理が施されていることが好ましい。これにより、ガラス基板への転写工程において、支持フィルムの剥離操作を容易に行うことができる。
また、転写フィルムには、膜形成材料層の表面に保護フィルム層が設けられてもよい。このような保護フィルム層としては、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリビニルアルコール系フィルムなどを挙げることができる。
【００２７】
本発明の組成物は、上記のように、支持フィルム上に膜形成材料層を形成して転写フィルムを製造する際に特に好適に使用することができるが、これらの用途に限定されるものではなく、従来において公知の膜形成材料層の形成方法、すなわち、スクリーン印刷法などによって当該組成物をガラス基板の表面に直接塗布し、塗膜を乾燥することにより膜形成材料層を形成する方法にも好適に使用することができる。ここに、スクリーン印刷法によるガラス基板への塗布工程に供されるガラスペースト組成物（本発明の組成物）の粘度としては、１０，０００〜２００，０００であることが好ましい。
【００２８】
【実施例】
以下、本発明の実施例について説明するが、本発明はこれらによって限定されるものではない。なお、以下において「部」は「重量部」を示す。
また、以下において使用されたガラス粉末の「平均粒子径および粒子径分布」、「ＢＥＴ比表面積」および「Ｂｌａｉｎ値」、並びに、形成された誘電体層における「Ｒａ中心線平均粗さ（Ｒａ）」は、下記のようにして測定した。
【００２９】
〔平均粒子径および粒子径分布〕
ガラス粉末に純水と中性洗剤３滴を加えて３分間超音波バス中で１００Ｗほど超音波予備分散をした後、「ＳＡＬＤ−２０００Ｊ」（島津製作所製）を用いて１分間本体内蔵超音波（４０Ｗ）をあてて、レーザー回折散乱法により、平均粒子径および粒子径分布を測定した。
【００３０】
〔ＢＥＴ比表面積〕
ガラス粉末をサンプルセルに入れ、２００℃で６０分間脱気処理を行った。その後、ＢＥＴ比表面積測定装置「ＧＥＭＩＮＩ２３６０」（島津製作所製）を用い、吸着ガスを窒素、キャリアガスをヘリウムとして、ＢＥＴ１点法により、ＢＥＴ比表面積を算出した。
【００３１】
〔Ｂｌａｉｎ値〕
恒圧通気式比表面積測定装置「ＳＳ−１００」（島津製作所製）を用い、測定を行った。計算式は、コゼニー・カーマン式を用いた。
【００３２】
〔Ｒａ中心線平均粗さ〕
表面形状測定装置「アルファステップ５００」（テンコールインスツルメンツ（株）製）を用い、針圧５．８ｍｇ、スキャンスピード１００μｍ／秒、スキャン処理２０００μｍで誘電体層表面をスキャンして、Ｒａ中心線平均粗さ（Ｒａ）を求めた。
【００３３】
＜実施例１＞
（１）ガラスペースト組成物の調製：
ガラス粉末として、酸化鉛６０重量％、酸化ホウ素１０重量％、酸化ケイ素２５重量％、酸化カルシウム５重量％の組成を有するＰｂＯ−Ｂ₂ Ｏ₃ −ＳｉＯ₂ −ＣａＯ系の混合物（軟化点５７０℃、旭硝子（株）製）からなり、平均粒子径が２μｍ、粒子径が１０μｍ以上である粒子の割合が２重量％、粒子径が０．７〜２．５μｍの範囲にある粒子の割合が５５重量％、ＢＥＴ比表面積が２．８ｍ² ／ｇ、Ｂｌａｉｎ値が１４０００であるガラス粉末１００部、結着樹脂として、ブチルメタクリレートとメチルメタクリレートとを共重合させて得られたアクリル樹脂（共重合割合：ブチルメタクリレート／メチルメタクリレート＝７０／３０（重量比）、ＧＰＣによるポリスチレン換算の重量平均分子量：８０，０００）２０部、溶剤としてプロピレングリコールモノメチルエーテル２０部を分散機を用いて混練することにより、粘度が７，０００ｃｐである本発明の組成物を調製した。
【００３４】
（２）転写フィルムの製造：
上記（１）で調製した本発明の組成物を、予め離型処理したポリエチレンテレフタレート（ＰＥＴ）よりなる支持フィルム（幅４００ｍｍ，長さ３０ｍ，厚さ３８μｍ）上にロールコータを用いて塗布し、形成された塗膜を１００℃で５分間乾燥することにより溶剤を除去し、これにより、厚さ５０μｍの膜形成材料層が支持フィルム上に形成されてなる転写フィルムを製造した。この転写フィルムについて、膜形成材料層の表面状態を顕微鏡を用いて観察したところ、ガラス粉末の凝集物、筋状の塗装跡、クレーター、ピンホールなどの膜欠陥は認められず、クレーター状のへこみも観察されなかった。
【００３５】
（３）膜形成材料層の転写：
２０インチパネル用のガラス基板の表面（バス電極の固定面）に、膜形成材料層の表面が当接されるよう、上記（２）で製造した転写フィルムを重ね合わせ、この転写フィルムを加熱ロールにより熱圧着した。ここで、圧着条件としては、加熱ロールの表面温度を１１０℃、ロール圧を３ｋｇ／ｃｍ² 、加熱ロールの移動速度を１ｍ／分とした。
熱圧着処理の終了後、膜形成材料層から支持フィルムを剥離除去した。これにより、ガラス基板の表面に膜形成材料層が転写されて密着した状態となった。
【００３６】
（４）膜形成材料層の焼成処理および誘電体層の評価：
上記（３）により膜形成材料層を転写形成したガラス基板を焼成炉内に配置し、炉内の温度を、常温から１０℃／分の昇温速度で５６０℃まで昇温し、５６０℃の温度雰囲気下３０分間にわたって焼成処理することにより、ガラス基板の表面に、無色透明なガラス焼結体よりなる誘電体層を形成した。
この誘電体層の形状を目視で観察したところ、ひび割れ、基板からの剥離などは認められなかった。
この誘電体層の膜厚（平均膜厚および公差）を測定したところ３０μｍ±１．０μｍの範囲にあり、膜厚の均一性に優れているものであった。
また、この誘電体層の中心線平均粗さ（Ｒａ）を測定したところ０．１μｍであり、表面平滑性に優れていることが確認された。
さらに、このようにして、誘電体層を有するガラス基板よりなるパネル材料を５台分作製し、形成された誘電体層の光透過率（測定波長６００ｎｍ）を測定したところ９０％であり、良好な透明性を有するものであることが認められた。
以上の結果をまとめて表１に示す。
【００３７】
＜実施例２〜５および比較例１〜５＞
表１に示す処方に従って、物性の異なるガラス粉末（酸化鉛６０重量％、酸化ホウ素１０重量％、酸化ケイ素２５重量％、酸化カルシウム５重量％の組成を有するＰｂＯ−Ｂ₂ Ｏ₃ −ＳｉＯ₂ −ＣａＯ系の混合物）を使用したこと以外は実施例１と同様にして本発明のガラスペースト組成物および比較用のガラスペースト組成物を調製した。
次いで、得られたガラスペースト組成物の各々を使用したこと以外は実施例１と同様にして転写フィルムを製造し、この転写フィルムにおける膜形成材料層の表面状態を観察した。
その後、得られた転写フィルムの各々を使用したこと以外は実施例１と同様にして、膜形成材料層の転写および膜形成材料層の焼成処理を行って、２０インチパネル用のガラス基板の表面に誘電体層（厚さ３０μｍ±１．０μｍ）を形成した。
【００３８】
実施例２〜５および比較例１〜５に係る組成物の各々について、▲１▼ 形成された誘電体層の形状を評価し、▲２▼ 当該誘電体層の中心線平均粗さ（Ｒａ）を測定し、▲３▼ 当該誘電体層の光透過率（６００ｎｍ）を測定した。
ここに、誘電体層の形状は、ひび割れ、基板からの剥離などの欠陥がなかった場合を「良好」と判定した。
以上の結果を表１に示す。
【００３９】
【表１】

【００４０】
【発明の効果】
本発明の組成物によれば下記のような効果が奏される。
（１）優れた表面平滑性（例えば、中心線平均粗さＲａが０．２μｍ以下）と、優れた無色透明性（高い光透過率）とを兼ね備えたガラス焼結体を形成することができ、当該ガラス焼結体は、ＰＤＰの誘電体層として好適である。
（２）比較的低温条件（６００℃以下）で行われる焼成によって結着樹脂を完全に分解除去することができ、これに由来する有機物質を含有しない無色透明性に優れたガラス焼結体を形成することができる。
（３）転写フィルムの製造に好適に使用することができる。
（４）膜形成材料層の転写性（ガラス基板に対する膜形成材料層の加熱接着性）に優れた転写フィルムを製造することができる。
【図面の簡単な説明】
【図１】交流型のプラズマディスプレイパネルの断面形状を示す模式図である。
【符号の説明】
１ ガラス基板
２ ガラス基板
３ 隔壁
４ バス電極
５ アドレス電極
６ 蛍光物質
７ 誘電体層
８ 保護層[0001]
BACKGROUND OF THE INVENTION
  The present inventionFor glass sintered body formationGlass paste compositionAnd transfer filmMore specifically, it can be suitably used for forming a dielectric layer or the like of a plasma display panel.For glass sintered body formationGlass paste compositionAnd transfer filmAbout.
[0002]
[Prior art]
Recently, a plasma display has attracted attention as a flat fluorescent display. FIG. 1 is a schematic view showing a cross-sectional shape of an AC type plasma display panel (hereinafter also referred to as “PDP”). In the figure, reference numerals 1 and 2 denote glass substrates facing each other, 3 denotes partition walls, and cells are partitioned by the glass substrate 1, glass substrate 2, and partition walls 3. 4 is a bus electrode fixed to the glass substrate 1, 5 is an address electrode fixed to the glass substrate 2, 6 is a fluorescent substance held in the cell, and 7 is a surface of the glass substrate 1 so as to cover the bus electrode 4. The formed dielectric layer 8 is a protective film made of, for example, magnesium oxide. The dielectric layer 7 is formed of a glass sintered body and has a thickness of 20 to 50 μm, for example.
[0003]
As a method for forming the dielectric layer 7, a paste-like composition (glass paste composition) containing glass powder, a binder resin and a solvent is prepared, and this glass paste composition is formed on the glass substrate 1 by screen printing. A method is known in which a film-forming material layer is formed by coating on the surface and drying, and then the film-forming material layer is baked to remove organic substances and sinter the glass powder.
[0004]
Here, as the binder resin constituting the glass paste composition, cellulose derivatives such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, urethane resin, melamine resin, etc. are known, Of these, ethyl cellulose is preferred from the viewpoints of dispersibility of glass powder, coating characteristics of the composition, ease of combustion, and the like (see, for example, JP-A-6-321619).
[0005]
Therefore, the thickness of the film forming material layer formed on the glass substrate 1 is 1 of the film thickness of the dielectric layer 7 to be formed in consideration of the reduction in the film thickness accompanying the removal of the organic substance in the baking process. For example, in order to set the thickness of the dielectric layer 7 to 20 to 50 μm, a film forming material layer having a thickness of about 30 to 100 μm is formed. There is a need.
On the other hand, when the glass paste composition is applied by screen printing, the thickness of the coating film formed by one application process is about 15 to 25 μm.
For this reason, in order to make the film forming material layer have a predetermined thickness, it is necessary to repeatedly apply (multiple printing) the glass paste composition to the surface of the glass substrate a plurality of times (for example, 2 to 7 times). There is.
[0006]
However, when the film forming material layer is formed by multiple printing using the screen printing method, the dielectric layer formed by firing the film forming material layer has a uniform film thickness (for example, tolerance is within ± 5%) ). This is because it is difficult to uniformly apply the glass paste composition to the surface of the glass substrate in the multiplex printing by the screen printing method. The larger the application area (panel size), the more the application times. The degree of variation in the film thickness in the dielectric layer increases. The panel material (glass substrate having the dielectric layer) obtained through the coating process by multiple printing has a variation in dielectric characteristics due to the variation in film thickness within the surface. This causes display defects (luminance unevenness) in the PDP.
Further, in the screen printing method, the mesh shape of the screen plate may be transferred to the surface of the film forming material layer, and the dielectric layer formed by firing such a film forming material layer has a smooth surface. It becomes inferior to.
[0007]
As a means for solving the above-mentioned problems when forming a film-forming material layer by a screen printing method, the present inventors applied a glass paste composition on a support film and dried the coating film to form a film. The surface of the glass substrate is formed by forming a material layer, transferring the film forming material layer formed on the support film onto the surface of the glass substrate on which the electrodes are fixed, and firing the transferred film forming material layer. Has proposed a method of manufacturing a PDP including a method of forming a dielectric layer (hereinafter referred to as “dry film method”) (see Japanese Patent Application No. 8-196304).
Here, as an example of the transfer process in the dry film method, a composite film (hereinafter referred to as “transfer film”) in which a film forming material layer is formed on a support film is applied to the surface (electrode fixing surface) of the glass substrate. After the superposition, the heating roller is moved onto the transfer film to heat-bond the film-forming material layer to the surface of the glass substrate, and then the support film from the film-forming material layer bonded and fixed to the surface of the glass substrate The method of peeling and removing can be mentioned.
And according to the manufacturing method of PDP including such a dry film method, a dielectric layer with favorable film thickness uniformity and surface smoothness can be formed.
This manufacturing method is also advantageous in that the transfer film, which is a material for forming the dielectric layer, can be rolled up and stored.
[0008]
[Problems to be solved by the invention]
However, in the case where a glass paste composition containing a conventionally known resin such as a cellulose derivative is applied onto a support film to form a film-forming material layer (manufacturing a transfer film), the film-forming material constituting the transfer film Since the layer does not have sufficient adhesiveness (heating adhesiveness) to the glass substrate, there is a problem that it is difficult to transfer from the support film to the surface of the glass substrate.
Further, from the viewpoint of exhibiting good electrical characteristics in the dielectric layer constituting the PDP, the dielectric layer is required to have further excellent surface smoothness.
Furthermore, the dielectric layer constituting the PDP is required to have high light transmittance and excellent colorless transparency.
[0009]
The present invention has been made based on the above situation.
The first object of the present invention is to provide a glass paste composition capable of forming a glass sintered body excellent in surface smoothness.
The second object of the present invention is to provide a glass paste composition capable of forming a glass sintered body which is more excellent in colorless transparency than before.
The third object of the present invention is that the binder resin can be completely decomposed and removed by a baking treatment performed at a relatively low temperature condition (600 ° C. or less), and it is colorless and transparent without containing an organic substance derived therefrom. The object is to provide a glass paste composition capable of forming an excellent glass sintered body.
A fourth object of the present invention is to provide a glass paste composition capable of forming a glass sintered body suitable as a dielectric layer of PDP.
A fifth object of the present invention is to provide a glass paste composition that can be suitably used for producing a transfer film.
The sixth object of the present invention is to provide a glass paste composition capable of producing a transfer film excellent in transferability of the film-forming material layer (heat adhesion of the film-forming material layer to the glass substrate). .
[0010]
[Means for Solving the Problems]
  Of the present inventionFor glass sintered body formationThe glass paste composition (A) has an average particle size of 0.5 to 3 μm, and a particle size distribution satisfies the conditions shown in the following (1) and (2): (B) Contains binder resin and (C) solventAnd the ratio of the glass powder is 50% by weight or more.It is characterized by that.
(1) The ratio of particles having a particle diameter of 10 μm or more is 10% by weight or less.
(2) The ratio of particles having a particle diameter in the range of 0.7 to 2.5 μm is 40% by weight or more.
  In the composition of the present invention,Binder resinAn acrylic resin is preferable.
  The transfer film of the present invention comprises a support film and a film-forming material layer formed on the support film, and the film-forming material layer contains the glass paste composition for forming a glass sintered body on the support film. It is characterized in that it is formed by applying to the surface.
[0011]
[Action]
(1) By controlling the average particle size and particle size distribution of the glass powder dispersed in the composition to a specific range, it has excellent surface smoothness and superior colorless transparency compared to before. A glass sintered body (for example, a PDP dielectric layer) can be formed.
(2) Since the acrylic resin is contained as the binder resin, the film-forming material layer to be formed exhibits excellent heat adhesion to the glass substrate. Therefore, when a transfer film is produced by applying the composition of the present invention on a support film, the obtained transfer film has excellent transferability of the film-forming material layer (transferability to a glass substrate). .
[0012]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, the present inventionFor glass sintered body formationThe glass paste composition will be described in detail.
  Of the present inventionFor glass sintered body formationThe glass paste composition contains glass powder, a binder resin made of an acrylic resin, and a solvent as essential components.
[0013]
<Constituent material of glass powder>
The glass powder constituting the composition of the present invention preferably has a softening point in the range of 400 to 600 ° C.
When the softening point of the glass powder is less than 400 ° C., the glass powder melts at a stage where organic substances such as the binder resin are not completely decomposed and removed in the baking process of the film forming material layer by the composition Therefore, a part of the organic substance remains in the formed dielectric layer, and as a result, the dielectric layer tends to be colored and the light transmittance tends to decrease. On the other hand, when the softening point of the glass powder exceeds 600 ° C., the glass substrate needs to be baked at a temperature higher than 600 ° C., so that the glass substrate is likely to be distorted.
Specific examples of suitable glass powder include: (1) lead oxide, boron oxide, silicon oxide (PbO-B₂O_Three-SiO₂System), (2) zinc oxide, boron oxide, silicon oxide (ZnO-B)₂O_Three-SiO₂System), (3) lead oxide, boron oxide, silicon oxide, aluminum oxide (PbO-B)₂O_Three-SiO₂-Al₂O_Three4) lead oxide, zinc oxide, boron oxide, silicon oxide (PbO-ZnO-B)₂O_Three-SiO₂System), (5) lead oxide, boron oxide, silicon oxide, calcium oxide (PbO-B)₂O_Three-SiO₂-CaO-based) and the like.
[0014]
<Average particle diameter of glass powder>
The average particle diameter of the glass powder constituting the composition of the present invention is usually 0.5 to 3 μm, preferably 1 to 2.5 μm.
When a glass paste composition having an average particle diameter of glass powder of less than 0.5 μm is used, a binder resin that is a dispersion medium for the glass powder when the film forming material layer made of the composition is fired. Is difficult to decompose and remove, and the organic substance remains in the finally formed glass sintered body (dielectric layer). As a result, the glass sintered body is colored or clouded, leading to a significant decrease in colorless transparency. On the other hand, when a glass paste composition having an average particle size of glass powder exceeding 3 μm is used, crater-like dents are frequently generated on the film-forming material layer of the composition, and this is formed by firing treatment. The glass sintered body (dielectric layer) does not have excellent surface smoothness (for example, the value of the center line average roughness Ra is 0.2 μm or less).
The “average particle diameter of the glass powder” refers to a value obtained from the particle diameter measured by the laser diffraction scattering method.
[0015]
<Particle size distribution of glass powder>
As the particle size distribution of the glass powder constituting the composition of the present invention, it is first necessary that the proportion of particles having a particle size of 10 μm or more is 10% by weight or less.
Even if the average particle diameter of the glass powder is in the range of 0.5 to 3 μm, if the proportion of coarse particles having a particle diameter of 10 μm or more exceeds 10% by weight, the glass sintered finally formed The body is inferior in surface smoothness.
Furthermore, as the particle size distribution of the glass powder, the proportion of particles having a particle size in the range of 0.7 to 2.5 μm is required to be 40% by weight or more.
Even if the average particle diameter of the glass powder is in the range of 0.5 to 3 μm and the ratio of coarse particles is 10% by weight or less, the ratio of the particles having a particle diameter in the range of 0.7 to 2.5 μm is If it is less than 40% by weight, the particle size distribution of the glass powder varies, and the film strength of the resulting transfer film becomes non-uniform, so that the formed glass sintered body may be cracked.
The “particle size distribution of the glass powder” refers to a value obtained from the particle size measured by the laser diffraction scattering method.
[0016]
The glass powder has a BET specific surface area of 1.0 to 5.5 m.²/ G is preferable. BET specific surface area is 1.0m²If it is less than / g, since the film strength of the transfer film obtained because the adsorption area of the binder resin in the glass paste composition is too small, the formed glass sintered body peels from the substrate, Cracks may occur. On the other hand, the BET specific surface area is 5.5 m.²When the amount exceeds / g, the adsorption between the glass powder and the binder resin is too strong, and it is difficult to remove the binder resin during the firing treatment and may remain in the glass sintered body.
[0017]
Moreover, it is preferable that the blain value of glass powder exists in the range of 3,000-20,000. Here, the “Blain value” is a specific surface area measured by an air permeation method, and is generally said to represent a specific surface area of aggregated secondary particles.
When the Blain value of the glass powder is less than 3,000, there are many agglomerated secondary particles in the glass paste composition, which may adversely affect the surface smoothness of the obtained glass sintered body. On the other hand, when the Blain value exceeds 20,000, the adsorption between the glass powder and the binder resin is too strong, and the binder resin becomes difficult to be removed during the firing treatment, and remains in the glass sintered body. May end up.
[0018]
  The proportion of the glass powder in the composition of the present invention is 50% by weight or more from the viewpoint of imparting further excellent colorless transparency (high light transmittance) to the formed glass sintered body.It is.
[0019]
<Binder resin>
In the composition of the present invention, the binder resin is preferably an acrylic resin.
When the acrylic resin is contained as the binder resin, the film-forming material layer to be formed exhibits excellent (heating) adhesion to the glass substrate. Therefore, when a transfer film is produced by applying the composition of the present invention on a support film, the obtained transfer film has excellent transferability of the film-forming material layer (transferability to a glass substrate). .
As such an acrylic resin, a (co) polymer that has a suitable adhesiveness and can bind glass powder and is completely oxidized and removed by the firing temperature (400 ° C. to 600 ° C.) of the film forming material. Selected from. The acrylic resin includes a homopolymer of a (meth) acrylate compound represented by the following general formula (1), two or more copolymers of a (meth) acrylate compound represented by the following general formula (1), And a copolymer of a (meth) acrylate compound represented by the following general formula (1) and another copolymerizable monomer.
[0020]
[Chemical 1]

[0021]
[In the formula, R¹Represents a hydrogen atom or a methyl group, R²Is monovalent organicBaseIndicates. ]
[0022]
Specific examples of the (meth) acrylate compound represented by the general formula (1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate , Isooctyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meta Acrylate, alkyl (meth) acrylates such as lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate;
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylates such as acrylates;
Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate;
Alkoxyalkyls such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, etc. ) Acrylate;
Polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene Polyalkylene glycol (meth) acrylates such as glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate;
Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl ( Cycloalkyl (meth) acrylates such as (meth) acrylate and tricyclodecanyl (meth) acrylate;
Examples thereof include benzyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate.
Among these, in the general formula (1), R²Is preferably a group containing an alkyl group or an oxyalkylene group, and particularly preferred (meth) acrylate compounds include methyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, and lauryl. Mention may be made of (meth) acrylate, isodecyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate.
The other copolymerizable monomer used for copolymerization with the (meth) acrylate compound is not particularly limited as long as it is a compound copolymerizable with the (meth) acrylate compound. For example, (meth) acrylic acid And unsaturated carboxylic acids such as vinyl benzoic acid, maleic acid, and vinyl phthalic acid; vinyl group-containing radical polymerizable compounds such as vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, butadiene, and isoprene. . In the acrylic resin constituting the composition of the present invention, the copolymer component derived from the (meth) acrylate compound represented by the general formula (1) is usually 70% by weight or more, preferably 90% by weight or more, more preferably 100% by weight.
The molecular weight of the binder resin constituting the composition of the present invention is preferably 2,000 to 300,000, more preferably 5,000 to 200,000 as a weight average molecular weight in terms of polystyrene by GPC. The
[0023]
The content ratio of the binder resin in the composition of the present invention is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the glass powder. When the proportion of the binder resin is too small, the glass powder cannot be reliably held by binding, whereas when this proportion is excessive, the firing process takes a long time or is formed. The glass sintered body (dielectric layer) to be produced does not have sufficient strength and film thickness.
[0024]
<Solvent>
As the solvent constituting the composition of the present invention, the affinity with the glass powder, the solubility of the binder resin are good, the glass paste composition can be imparted with an appropriate viscosity, and is dried. It is preferable that it can be easily removed by evaporation.
Particularly preferred solvents include ketones, alcohols and esters (hereinafter referred to as “specific solvents”) having a normal boiling point (boiling point at 1 atm) of 100 to 200 ° C.
Specific examples of the specific solvent include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone, and cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol, and diacetone alcohol. Ether ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; saturated aliphatic monocarboxylic acids such as n-butyl acetate and amyl acetate Alkyl esters; lactic acid esters such as ethyl lactate and lactic acid-n-butyl; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl acetate Examples include ether esters such as diacetate and ethyl-3-ethoxypropionate. Among these, methyl butyl ketone, cyclohexanone, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, lactic acid Ethyl, ethyl-3-ethoxypropionate and the like are preferable. These specific solvents can be used alone or in combination of two or more.
Specific examples of solvents other than the specific solvent include turpentine oil, ethyl cellosolve, methyl cellosolve, terpineol, butyl carbitol acetate, butyl carbitol, isopropyl alcohol, benzyl alcohol and the like.
The content ratio of the solvent in the composition of the present invention is preferably 5 to 50 parts by weight, more preferably 100 parts by weight of the glass powder, from the viewpoint of maintaining the viscosity of the composition in a suitable range. 10 to 40 parts by weight.
Further, the content ratio of the specific solvent with respect to the total solvent is preferably 50% by weight or more, and more preferably 70% by weight or more.
[0025]
  Of the present inventionFor glass sintered body formationIn addition to the above essential components, the glass paste composition contains various additives such as dispersants, tackifiers, plasticizers, surface tension modifiers, stabilizers, antifoaming agents, and dispersants as optional components. May be.
  An example of a preferred glass paste composition is composed of a mixture of 50 to 80% by weight of lead oxide, 5 to 20% by weight of boron oxide, 10 to 25% by weight of silicon oxide, and 0 to 5% by weight of calcium oxide. The ratio of particles having a diameter of 2 μm, a particle diameter of 10 μm or more is 1% by weight, the ratio of particles having a particle diameter in the range of 0.7 to 2.5 μm is 90% by weight, and the BET specific surface area is 2.5 m.²/ G, 100 parts by weight of glass powder having a Blain value of 10,000, 10 to 30 parts by weight of polybutyl methacrylate (acrylic resin), and 10 to 50 parts by weight of propylene glycol monomethyl ether (solvent) The composition which does is mentioned.
  The composition of the present invention can be prepared by kneading the glass powder, binder resin, solvent and optional components using a kneading / dispersing machine such as a roll kneader, a mixer, a homomixer, or a sand mill.
  The composition of the present invention prepared as described above is a paste-like composition having fluidity suitable for coating.
[0026]
The composition of the present invention can be particularly suitably used for producing a transfer film. This transfer film is composed of a support film and a film forming material layer formed on the support film, and is a composite material used in a dielectric layer forming step by a dry film method. Here, the viscosity of the glass paste composition (composition of the present invention) used for the coating step on the support film by the dry film method is preferably 1,000 to 30,000.
The support film constituting the transfer film is preferably a resin film having heat resistance and solvent resistance and flexibility. Since the support film has flexibility, the composition of the present invention can be applied by a roll coater, a blade coater, etc., and the film-forming material layer can be stored and supplied in a rolled state. it can. Examples of the resin that forms the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose. The thickness of the support film is, for example, 20 to 100 μm.
The film-forming material layer constituting the transfer film can be formed by applying the composition of the present invention on the support film, drying the coating film, and removing part or all of the solvent.
As a method of applying the composition of the present invention on a support film, it is preferable that a film having a large film thickness (for example, 20 μm or more) excellent in film thickness uniformity can be efficiently formed, Specifically, a coating method using a roll coater, a coating method using a blade coater, a coating method using a curtain coater, a coating method using a wire coater, and the like can be mentioned as preferable examples.
In addition, it is preferable that the mold release process is given to the surface of the support film with which the composition of this invention is apply | coated. Thereby, the peeling operation of a support film can be easily performed in the transfer process to a glass substrate.
In addition, the transfer film may be provided with a protective film layer on the surface of the film forming material layer. Examples of such a protective film layer include a polyethylene terephthalate film, a polyethylene film, and a polyvinyl alcohol film.
[0027]
As described above, the composition of the present invention can be particularly preferably used when a film-forming material layer is formed on a support film to produce a transfer film, but is not limited to these applications. In the conventional method for forming a film-forming material layer, that is, a method for forming the film-forming material layer by directly applying the composition to the surface of the glass substrate by screen printing or the like and drying the coating film. Can also be suitably used. Here, the viscosity of the glass paste composition (the composition of the present invention) used for the coating step on the glass substrate by the screen printing method is preferably 10,000 to 200,000.
[0028]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “part” means “part by weight”.
Further, “average particle size and particle size distribution”, “BET specific surface area” and “Blain value” of the glass powder used below, and “Ra centerline average roughness (Ra) in the formed dielectric layer” Was measured as follows.
[0029]
[Average particle size and particle size distribution]
After adding 3 drops of pure water and neutral detergent to the glass powder and pre-dispersing the ultrasonic wave for about 100 W in an ultrasonic bath for 3 minutes, using “SALD-2000J” (manufactured by Shimadzu Corporation) for 1 minute with built-in ultrasonic (40 W) was applied, and the average particle size and particle size distribution were measured by a laser diffraction scattering method.
[0030]
[BET specific surface area]
Glass powder was put into a sample cell and degassed at 200 ° C. for 60 minutes. Then, using a BET specific surface area measuring device “GEMINI 2360” (manufactured by Shimadzu Corporation), the BET specific surface area was calculated by the BET one-point method using nitrogen as the adsorption gas and helium as the carrier gas.
[0031]
[Blain value]
The measurement was performed using a constant pressure aeration type specific surface area measuring device “SS-100” (manufactured by Shimadzu Corporation). As the calculation formula, the Cozeny-Kerman formula was used.
[0032]
[Ra centerline average roughness]
Using a surface shape measuring device “Alphastep 500” (manufactured by Tencor Instruments Co., Ltd.), scanning the surface of the dielectric layer with a needle pressure of 5.8 mg, a scanning speed of 100 μm / second, and a scanning process of 2000 μm, the Ra center line average Roughness (Ra) was determined.
[0033]
<Example 1>
(1) Preparation of glass paste composition:
As a glass powder, PbO-B having a composition of 60% by weight of lead oxide, 10% by weight of boron oxide, 25% by weight of silicon oxide, and 5% by weight of calcium oxide.₂O_Three-SiO₂A CaO-based mixture (softening point 570 ° C., manufactured by Asahi Glass Co., Ltd.), the average particle size is 2 μm, the proportion of particles having a particle size of 10 μm or more is 2% by weight, and the particle size is 0.7-2. The proportion of particles in the range of 5 μm is 55% by weight and the BET specific surface area is 2.8 m.²/ G, 100 parts of glass powder having a Blain value of 14000, acrylic resin obtained by copolymerizing butyl methacrylate and methyl methacrylate as a binder resin (copolymerization ratio: butyl methacrylate / methyl methacrylate = 70/30 ( (Weight ratio), 20 parts by weight of polystyrene-equivalent molecular weight by GPC: 80,000) The composition of the present invention having a viscosity of 7,000 cp by kneading 20 parts of propylene glycol monomethyl ether as a solvent using a disperser. A product was prepared.
[0034]
(2) Production of transfer film:
The composition of the present invention prepared in (1) above was applied on a support film (width 400 mm, length 30 m, thickness 38 μm) made of polyethylene terephthalate (PET), which had been subjected to release treatment in advance, using a roll coater, The formed coating film was dried at 100 ° C. for 5 minutes to remove the solvent, thereby producing a transfer film in which a film-forming material layer having a thickness of 50 μm was formed on the support film. For this transfer film, the surface state of the film-forming material layer was observed with a microscope, and no film defects such as agglomerates of glass powder, streaked paint marks, craters, and pinholes were observed, and crater-like dents were observed. Was also not observed.
[0035]
(3) Transfer of film forming material layer:
The transfer film manufactured in (2) above is overlaid on the surface of the glass substrate for 20-inch panels (fixing surface of the bus electrode) so that the surface of the film-forming material layer comes into contact therewith. Was thermocompression bonded. Here, as pressure bonding conditions, the surface temperature of the heating roll is 110 ° C., and the roll pressure is 3 kg / cm.²The moving speed of the heating roll was 1 m / min.
After the thermocompression treatment, the support film was peeled off from the film forming material layer. As a result, the film forming material layer was transferred and adhered to the surface of the glass substrate.
[0036]
(4) Firing treatment of film forming material layer and evaluation of dielectric layer:
The glass substrate on which the film forming material layer is transferred and formed by the above (3) is placed in a firing furnace, and the temperature in the furnace is increased from normal temperature to 560 ° C. at a temperature increase rate of 10 ° C./min. A dielectric layer made of a colorless and transparent glass sintered body was formed on the surface of the glass substrate by firing for 30 minutes in a temperature atmosphere.
When the shape of the dielectric layer was visually observed, no cracks, peeling from the substrate, etc. were observed.
When the film thickness (average film thickness and tolerance) of this dielectric layer was measured, it was in the range of 30 μm ± 1.0 μm, and the film thickness was excellent.
Moreover, when the center line average roughness (Ra) of this dielectric material layer was measured, it was 0.1 micrometer, and it was confirmed that it is excellent in surface smoothness.
Further, in this way, five panel materials made of a glass substrate having a dielectric layer were prepared, and the light transmittance (measurement wavelength 600 nm) of the formed dielectric layer was measured. It was recognized that it has a high transparency.
The above results are summarized in Table 1.
[0037]
<Examples 2-5 and Comparative Examples 1-5>
According to the formulation shown in Table 1, glass powders having different physical properties (PbO-B having a composition of 60% by weight of lead oxide, 10% by weight of boron oxide, 25% by weight of silicon oxide, and 5% by weight of calcium oxide)₂O_Three-SiO₂A glass paste composition of the present invention and a comparative glass paste composition were prepared in the same manner as in Example 1 except that the -CaO-based mixture) was used.
Next, a transfer film was produced in the same manner as in Example 1 except that each of the obtained glass paste compositions was used, and the surface state of the film-forming material layer in this transfer film was observed.
Thereafter, the transfer of the film-forming material layer and the baking treatment of the film-forming material layer were performed in the same manner as in Example 1 except that each of the obtained transfer films was used, and the surface of the glass substrate for a 20-inch panel. A dielectric layer (thickness 30 μm ± 1.0 μm) was formed.
[0038]
For each of the compositions according to Examples 2 to 5 and Comparative Examples 1 to 5, (1) the shape of the formed dielectric layer was evaluated, and (2) the center line average roughness (Ra) of the dielectric layer. (3) The light transmittance (600 nm) of the dielectric layer was measured.
Here, the shape of the dielectric layer was determined to be “good” when there were no defects such as cracks and peeling from the substrate.
The results are shown in Table 1.
[0039]
[Table 1]

[0040]
【The invention's effect】
According to the composition of the present invention, the following effects are exhibited.
(1) A glass sintered body having excellent surface smoothness (for example, centerline average roughness Ra is 0.2 μm or less) and excellent colorless transparency (high light transmittance) can be formed. The glass sintered body is suitable as a PDP dielectric layer.
(2) A glass sintered body that is capable of completely decomposing and removing the binder resin by firing performed under relatively low temperature conditions (600 ° C. or less), and that is free of organic substances derived therefrom and that has excellent colorless transparency. Can be formed.
(3) It can be used suitably for manufacture of a transfer film.
(4) A transfer film excellent in transferability of the film-forming material layer (heat adhesion of the film-forming material layer to the glass substrate) can be produced.
[Brief description of the drawings]
FIG. 1 is a schematic view showing a cross-sectional shape of an AC type plasma display panel.
[Explanation of symbols]
1 Glass substrate
2 Glass substrate
3 Bulkhead
4 bus electrodes
5 Address electrodes
6 Fluorescent substances
7 Dielectric layer
8 Protective layer

Claims (3)

(A) An average particle diameter of 0.5 to 3 μm, and a particle diameter distribution satisfying the conditions shown in the following (1) and (2): (B) a binder resin and (C ) A glass paste composition for forming a sintered glass , comprising a solvent and having a glass powder content of 50% by weight or more .
(1) The ratio of particles having a particle diameter of 10 μm or more is 10% by weight or less.
(2) The ratio of particles having a particle diameter in the range of 0.7 to 2.5 μm is 40% by weight or more. The glass paste composition for forming a glass sintered body according to claim 1, wherein the binder resin is an acrylic resin. It is comprised by the support film and the film formation material layer formed on the said support film, and the said film formation material layer supports the glass paste composition for glass sintered compact formation of Claim 1 or Claim 2 as a support film. A transfer film formed by coating on a transfer film.

Images