1296567 • (1) 玖、發明說明 【發明所屬之技術領域】 本發明有關電漿顯示器面板（PDP )之介電體層，特 別是有關爲形成後面板用白色介電體層用之組成物及裸片 (green sheet)，以及使用裸片所形成之具有介電體層的 PDP構件。 【先前技術】 代表性影像顯示裝置而言，周知有使用液晶顯示、電 致發光（electroluminescent)顯示，或電漿顯示者。在此 種影像顯示裝置之中，近年來使用電漿顯示的PDP特別 受矚目，而爲改進此種裝置之高品質化、低耗電化、薄型 化、低價格化等方面之性能正在進行種種硏究。 第1圖，係表示PDP構造之一例的模式性剖面圖。 如第1圖所示，PDP具有將成爲光之釋放側的前面板用玻 璃基板1及背面板用玻璃基板2之一對玻璃基板，在各玻 璃基板內面分別形成有互相正交的透明電極3及位址電極 。透明電極3及位址電極5，係分別被透明介電體層5及 白色介電體層6所覆蓋，再者透明介電體層5則設置有保 護膜7。在如上述所構成的玻璃基板1與基板2之間，形 成有被隔板8所隔開的放電空間（像素），而對每一個像 素設置有螢光體9。 爲實現高品質之PDP起見，透明介電體層5及白色 介電體層6，需要具有均勻的厚度，且其表面必須爲平滑 1296567 • (2) 者。如介電體層之均勻性及表面平滑性不足時，則會有不 能保持介電體層之絕緣性，或在介電特性方面產生偏差而 成爲PDP上的顯示缺陷之原因。 又，如爲防止PDP放電時因電壓而發生單元（cell) 缺陷起見，介電體層需要具有優異的耐電壓特性。PDP之 介電體層，一般對0.5kv以上之電壓需要具有耐性。 介電體層，係在玻璃基板上設置介電材料之塗佈層， 接著’將塗佈層予以燒成即可形成。因此，玻璃基板上所 設置的塗佈層需要爲均勻且平滑。塗佈方法之一例，周知 有絲網印刷法（screen printing )。在利用絲網印刷法而 形成介電體層時，則重複進行在玻璃基板上印刷含有玻璃 料（glass frit )及樹脂的糊質，接著予以乾燥的過程。最 後將形成在玻璃基板上的塗佈層予以燒成，即可形成介電 體層。 然而，由於絲網印刷法係所謂濕式方法之故，一次可 形成的塗佈層之膜厚自然有其限度。又，爲塗佈層之厚膜 化時，需要重複進行在印刷糊質後使溶劑揮發，進而印刷 糊質的操作之多重印刷。因此，不僅作業效率差，且在塗 佈層中有殘留溶劑的可能性。其結果，不僅塗佈所需成本 高漲，殘留溶劑對塗佈層有不良影響，因而最終有引起介 電體層之性能降低之虞。 鑑於如此的狀況，則有將介電材料預先作成片材狀者 設置在基板上之幾種方法的報導。例如，在日本專利特開 昭6 1 - 22 6 82號公報中，揭示有在陶瓷基板上形成玻璃層 1296567 (3) 的施釉（glazed )陶瓷基板之製造方法。在此方法中，係 藉由：在帶（belt )或薄膜上將含有玻璃料或能玻璃化的 物質之分散體進行成膜以形成含有玻璃料或可玻璃化之物 質的裸片的過程，及在陶瓷基板上壓貼所得的裸片的過程 ，及接著將此等加熱後將裸片熔融固貼在陶瓷基板上的過 程，而在陶瓷基板上形成玻璃層者。惟如照此方法，則有 對陶瓷基板的裸片之密貼力較弱的問題。 又，在日本專利特開昭63— 197640號公報及日本專 利特開昭64 - 73086號公報中，揭示有具有：以玻璃料及 黏合劑爲主成份，必要時添加無機粉末以形成粉末片材的 過程，及介由感壓性黏接劑層而將粉末片材在要被覆之物 體上加壓層合的過程，及接著燒成所得的層合物的過程， 的塗佈方法。然而，如照此方法，由於需要另外多設置感 壓性黏接劑層之故，製造過程將呈繁雜。又，在燒成過程 中如感壓性黏接劑成份被熱分解的情形，則因熱分解所發 生的氣體而產生玻璃層之膨脹，以致有作爲介電體製品之 品質會低落的問題。 再者，爲解決上述問題，日本專利特開平 1 〇 -1 829 1 9號公報中，揭示有：以特定之比例含有聚甲基丙 烯酸酯及具有特定粒徑的玻璃粉末的透明介電體層用組成 物，以及使用由此種組成物而成的乾式薄膜的透明介電體 層之製造方法。又，在日本專利特開平9 — 1 02273號公報 中，揭示有：在陶瓷基板表面設置由含有玻璃粉末、黏合 樹脂以及溶劑的糊質狀組成物所形成的膜形成材料層，並 -9 - 1296567 • (4) 將此層燒成即可在陶瓷基板表面形成介電體層的PDP之 製造方法。 然而，在上述之任一種方法，經常是並非在調製介電 體層用組成物後馬上將該等加工爲片材狀，而係組成物仍 多以經調製後之狀態保持或交付運輸。如組成物被經久放 置，則組成物中所含粒子之分散性將降低，特別是玻璃料 等高比重之粒子即容易發生二次凝聚。結果，將分散狀態 惡化之組成物加工成片材狀，使用此等組成物以形成介電 體層時，所得介電體層之缺陷較多，而難於獲得作爲介電 體所需之特性。 【發明內容】 因而，本發明之課題，係以提供一種均勻性及平滑性 優異，耐電壓特性優異的介電體層可予形成且玻璃料之分 散性可予提高的介電體層用組成物，以及由這種組成物而 成的介電體層用裸片及PDP用構件者。 本發明之電漿顯示面板介電體層用組成物，其特徵爲 :含有至少含有玻璃成份之玻璃料、分散劑、熱分解性黏 合劑、以及溶劑，而上述分散劑係聚羧酸系高分子化合物 〇 在此，上述聚羧酸系高分子化合物，較佳爲選自α -烯烴/馬來酸酐共聚物之部份酯、脂肪族聚羧酸鹽、以及 脂肪族聚羧酸特殊聚矽氧烷而成群者。 上述分散劑之含量，以組成物之全重量爲基準時，較 -10- 1296567 ‘ （5) 佳爲在0·01至5.0重量％之範圍。 上述玻璃料，較佳爲再含有陶瓷塡料。 上述玻璃料之最大粒徑，較佳爲在分散狀態下爲20μ m以下。 本發明之電漿顯示器面板之介電體層用裸片，其特徵 爲：將上述本發明之介電體層用組成物塗佈在支持體上， 接著，加以乾燥而製得者。 本發明之電漿顯示器用構件之特徵爲：具有玻璃基板 ，及在該玻璃基板之一個主面上所設置之由上述本發明之 介電體層用組成物而成的介電體層。 參照所附圖面之下，由下列實施形態即可更明瞭本發 明之目的、效果、特性以及優點。 【實施方式】 以下，就本發明更詳細地加以說明。 本發明之第1狀態，係關於爲形成PDP介電體層用 的組成物。本發明之介電體層用組成物之特徵爲··含有； 至少含有玻璃成份的玻璃料、熱分解黏合劑、溶劑、以及 作爲分散劑所選擇的聚羧酸系高分子化合物。 本發明之介電體層用組成物之特徵爲：爲改善玻璃料 之分散性，而將聚羧酸系高分子化合物作爲分散劑使用。 在此，本說明書中所使用之用語「聚羧酸系高分子化合物 」係指包含α -烯烴/馬來酸酐共聚物之部份酯、脂肪族 聚錢酸鹽、以及脂肪族聚竣酸特殊聚砂氧院等之，在分子 -11 - 1296567 (6) 中具有複數個羧酸基的高分子化合物之意。這種聚羧酸系 高分子化合物，與矽烷偶合劑及一般性表面活性劑等周知 之分散劑比較時，係能使玻璃料等高比重之粒子良好地分 散者。特別是，α -烯烴/馬來酸酐共聚物之部份酯可呈 現優異的分散效果。 因而，將聚羧酸系高分子化合物作爲分散劑使用，即 可改善介電體層用組成物中玻璃料之分散性以保持組成物 爲良好的分散狀態。亦即，可抑制玻璃料凝聚以形成二次 粒子的現象。其結果，能改善介電體層中介電特性之偏差 ，且能提升介電體層之耐電壓。 分散劑之含量，以介電體層用組成物之全重量爲基準 ，較佳爲在0.01至5 ·0重量％之範圍。如分散劑之含量在 0·0 1重量％以下，則即使利用分散機處理組成物，玻璃料 仍然不能被均均分散的狀態。又，如分散劑之含量超過 5 ·0重量％，則在燒成後分散劑仍然殘留在介電體層內而 將成爲耐電壓低落的原因。 組成物中所含的玻璃料至少含有玻璃成份，必需時可 再含陶瓷塡料。在此，本發明書中所使用的用語「玻璃料 」’係指當燒成組成物以形成介電體層時，在介電體層中 所含的主要無機成份之總稱之意。 玻璃料所含的玻璃成份而言，可利用作爲玻璃成份一 般所周知者。可例舉·· Pb〇 - β2ο3 (氧化鉛一氧化硼）系 玻璃、Pb0—B203— Si02 (氧化鉛一氧化硼一氧化矽）系 玻璃、PbO — b2〇3 — Si〇2 — a1203 (氧化鉛—氧化硼—氧化 -12- 1296567 (7) 矽一氧化鋁）系玻璃、ZnO — B2〇3 — Si02 (氧化鋅一氧化 硼一氧化矽）系玻璃、PbO — ZnO — B2〇3 — Si02 (氧化鉛 —氧化鋅—氧化硼—氧化矽）系玻璃、Na20— B2〇3 — Si02 (氧化鈉一氧化硼—氧化矽）系玻璃、BaO — CaO - Si02 (氧化鋇-氧化鈣—氧化矽）系玻璃等，較佳爲PbO -b2o3—si〇2—ai2o3系玻璃。更具體而言，玻璃料之玻璃 成份較佳爲由30至75重量％之PbO，及1至40重量％之 B2O3，及1至40重量％之 Si〇2，及 1至 10重量％之 Al2〇3而成。作爲好用的一例，可舉：由60重量％之PbO ，及10重量％之B2〇3，及25重量％之Si02，及5重量％ 之ai2o3所構成的玻璃成份。玻璃成份之粒徑並不特別限 定。惟在組成物之調製時，爲達成良好的分散狀態而本發 明中好用的玻璃成份之平均粒徑爲0 · 5至5 μ m之範圍。 在形成有設置於PDP背面側的白色介電體層時，作 爲玻璃料，除玻璃成份之外，再添加陶瓷塡料成份。能在 本發明中使用的陶瓷塡料成份而言，可舉：Ti02 (氧化鈦 )、Al2〇3 (氧化鋁）、Si02 (氧化矽）以及Zr02 (鍩） 等。雖無特別限定，惟較佳爲Ti〇2及ai2o3。塡料之粒徑 並無特別限定。但在組成物之調製中爲達成良好的分散狀 態起見，本發明中好用的陶瓷塡料成份之平均粒徑爲在 〇·1至5μιη之範圍。 ， 玻璃料中玻璃成份與陶瓷塡料成份之比例，以該等全 重量爲基準，係玻璃成份爲50至1〇〇重量。/。及陶瓷塡料 成份爲50至〇重量％。較佳爲，在背面（白色）介電體 -13- 1296567 (8) 層用組成物的情形，則爲玻璃成份在5 0至9 0重量％及陶 瓷塡料成份在50至10重量％。又，在前面（透明）介電 體層用組成物的情形，較佳爲玻璃成份在1 〇 〇重量。/。及陶 瓷塡料成份在〇重量％。以玻璃料而言，以組成物之全重 量爲基準，可含有40至80重量％之範圍。 本發明所使用的熱分解性黏合劑，係在介電體層用組 成物賦與對玻璃基板的黏接性者。雖並無特別限定，惟作 爲好用的熱分解性黏合劑之一例，可舉丙烯酸樹脂。丙烯 酸樹脂中可包含：（甲基）丙烯酸酯化合物之單獨聚合物 、（甲基）丙烯酸酯化合物之2種以上共聚物、（甲基） 丙烯酸酯化合物與其他共聚性單體間之共聚物。 (甲基）丙烯酸酯化合物之具體例而言，可舉：（甲 基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸 丙酯、（甲基）丙烯酸異丙酯、（甲基）丙烯酸丁酯、（ 甲基）丙烯酸異丁酯、（甲基）丙烯酸第三丁酯、（甲基 )丙烯酸戊酯、（甲基）丙烯酸正戊酯、（甲基）丙烯酸 異戊酯、（甲基）丙烯酸己酯、（甲基）丙烯酸庚酯、（ 甲基）丙烯酸辛酯、（甲基）丙烯酸異辛酯、（甲基）丙 烯酸2—乙基己酯、（甲基）丙烯酸乙基己酯、（甲基） 丙烯酸壬酯、（甲基）丙烯酸癸酯、（甲基）丙烯酸異癸 酯、（甲基）丙烯酸十一烷酯、（甲基）丙烯酸十二烷酯 、（甲基）丙烯酸月桂酯、（甲基）丙烯酸硬脂醯酯、（ 甲基）丙烯酸異硬脂醯酯等之（甲基）丙烯酸烷酯；（甲 基）丙烯酸羥乙酯、（甲基）丙烯酸2—羥基丙酯、（甲 -14- 1296567 (9) 基）丙烯酸4一羥基丁酯、（甲基）丙烯酸3-羥基丙酯 、（甲基）丙烯峻2-羥基丁酯、（甲基）丙烯酯3—羥基 丁酯等之（甲基）丙烯酸羥基烷基； (甲基）丙烯酸苯氧基乙酯、（甲基）丙烯酸2—羥 基一 3-苯氧基丙酯等之（甲基）丙烯酸苯氧基烷酯； (甲基）丙烯酸2 —甲氧基乙酯、（甲基）丙烯酸2 一乙氧基乙酯、（甲基）丙烯酸2—丙氧基乙酯、（甲基 )丙烯酸2-丁氧基乙酯、（甲基）丙烯酸2—甲氧基丁 酯等之（甲基）丙烯酸烷氧基烷酯； 聚乙二醇單（甲基）丙烯酸酯、乙氧基二乙二醇（甲 基）丙烯酸酯、甲氧基聚乙二醇（甲基）丙烯酸酯、苯氧 基聚乙二醇（甲基）丙烯酸酯、壬基苯氧基聚乙二醇（甲 基）丙烯酸酯、聚丙二醇單（甲基）丙烯酸酯、甲氧基聚 丙二醇（甲基）丙烯酸酯、乙氧基聚丙二醇（甲基）丙烯 酸酯、壬基苯氧基聚丙二醇（甲基）丙烯酸酯等之聚烷二 醇（甲基）丙烯酸酯； 環己基（甲基）丙烯酸酯、4 一丁基環己基（甲基） 丙烯酸酯、二環戊烷基（甲基）丙烯酸酯、二環戊烯基（ 甲基）丙烯酸酯、二環戊二烯基（甲基）丙烯酸酯、冰片 基（甲基）丙烯酸酯、異冰片基（甲基）丙烯酸酯、三環 癸烷基（甲基）丙烯酸酯等之環烷基（甲基）丙烯酸酯； 苄基（甲基）丙烯酸酯、四氫呋喃（甲基）丙烯酸酯 等。其中較佳爲（甲基）丙烯酸烷酯或（甲基）丙烯酸烷 氧基烷酯，特佳之（甲基）丙烯酸酯而言，可舉··（甲基 -15- 1296567 (10) )丙燃酸丁酯、（甲基）丙烯酸乙基己酯、（甲基）丙烯 酸月桂酯、（甲基）丙烯酸異癸酯、（甲基）丙烯酸2 -乙基己酯、以及（甲基）丙烯酸2 —乙基乙酯。 其他共聚物單體而言，衹要是能與上述（甲基）丙烯 酸酯化合物進行共聚之化合物，則並不特別限制，惟可例 舉：（甲基）丙烯酸、乙烯基安息香酸、馬來酸、乙烯基 酞酸等之不飽和羧酸類；乙烯基苄基甲醚、乙烯基縮水甘 油醚、苯乙烯、α —甲基苯乙烯、丁二烯、異戊二烯等含 有乙烯基之自由基聚合性化合物。 熱分解性黏合劑之含量，並不特別限定，惟以介電體 層用組成物之全重量爲基準時，較佳爲在5至30重量％ 之範圍。 本發明所使用的溶劑，較佳爲能對介電體層用組成物 賦與適當的流動性或可塑性、良好的膜形成性者。可使用 的溶劑而言，可例舉：醚類、酯類、醚型酯類、酮類、酮 型酯類、醯胺類、醯胺型酯類、內醯胺類、內酯類、亞碼 類、碼類、烴類、鹵化烴類等。較佳溶劑之具體例中包含 :甲苯、乙酸乙酯、以及甲基乙基酮。可以按單獨或組合 2種以上之方式使用上述溶媒。溶劑之含量，以介電體層 用組成物之全重量作爲基準，係在1 5至5 5重量％之範圍 〇 本發明中，作爲添加劑而可在介電體層用組成物中再 含有：如己二酸酯系可塑劑等之可塑劑、粘接賦與劑、保 存安定劑、消泡劑、熱分解促進劑以及防氧化劑等之添加 -16- 1296567 (11) 劑。此等添加劑，並不特別限定，而可適當選擇在此領域 常用者。 雖並不特別限定，惟本發明之介電體層用組成物之一 個較佳實施狀態，係含有：含有Pb0/B203/Si02/Al203 = 60/1 0/25/5重量％之玻璃成份及Al203/Ti02之陶瓷塡料成 份的玻璃料、及2 -乙基己基丙烯酸酯（熱分解性黏合劑 )、及α -烯烴/馬來酸酐共聚物之部份酯（分散劑）、 及己二酸二丁酯（可塑劑），以及甲苯（溶劑）的組成物 。又，本發明之介電體層用組成物之其他一個較佳實施形 態，係含有··含有 PbO/B2O3/SiO2/Al2O3 = 60/1 0/25/5 重 量％之玻璃成份的玻璃料、及2-乙基己基丙烯酸酯（熱 分解性黏合劑）、及α -烯烴/馬來酸酐共聚物之部份酯 (分散劑）、及己二酸二丁酯（可塑劑）、以及甲苯（溶 劑）的組成物。 本發明之介電體層用組成物，係將玻璃料、分散劑、 熱分解性黏合劑以及必要時所添加的各種添加劑與溶劑一 起預混後，可使用例如，球磨、珠磨、三輥硏磨機、捏合 機等之分散機按機械方式使其分散以調製。爲使組成物之 分散狀態更爲均勻起見，亦可延長分散機所處理的時間， 或選擇更能有效分散的分散機。 分散狀態下的玻璃料，係由於聚羧酸系高分子化合物 之優異的分散作用，使一次粒子被均勻分散而可抑制二次 凝聚。玻璃料之最大粒徑在分散狀態下較佳爲20μιη以下 。如玻璃料之最大粒徑超過2 0 μ m，則由如此組成物而成 -17- 1296567 (12) 的介電體層，將在其表面容易產生針孔等之缺陷，以致難 於獲得所需要的耐電壓特性。 如上述，由於本發明之介電體層用組成物係作爲分散 劑而使用聚羧酸系高分子化合物之故，可適當調節玻璃料 之分散狀態以達成良好的分散狀態。再者，由於聚羧酸系 高分子化合物之優異的分散作用而能防止玻璃料之二次凝 聚之故，能將剛調製組成物時良好分散狀態長時間維持。 因而，使用本發明之介電體層用組成物，即能形成耐電壓 及介電特性優異的介電體層。 本發明之第2狀態，係關於爲形成P D P之介電體層 所使用的裸片。本發明之裸片之特徵爲：將上述所說明的 本發明之介電體層用組成物塗佈在支持體上，接著，加以 乾燥即可製得。 本發明之裸片，更具體而言，係將至少含有玻璃料、 聚羧酸系高分子化合物、熱分解性黏合劑，以及溶劑的組 成物充份混合以使玻璃料均勻分散，依刮刀塗佈法或壓模 塗佈法等方法將所得的分散液塗佈在聚對苯二甲酸乙二醇 酯製薄膜等之支持體上，使其乾燥並去除溶劑而作成薄膜 狀者。 由於支持體上之裸片，係具有粘接性，在可撓性、加 工性以及操作處理性優異之故，能容易轉印在玻璃基板上 。在此，「具有粘接性」係指在室溫或加溫下當裸片接觸 於玻璃基板時，裸片將密貼在玻璃基板上並被固定之意。 在此，爲改善將裸板轉印至玻璃基板上時之剝離性起見， -18- 1296567 (13) 支持體較佳爲經聚矽氧烷等表面處理者。被轉印至玻璃基 板上的裸板，經過燒成後將形成以玻璃成份爲主成份的介 電體層。 由於使用上述裸片以形成介電體層之故，可依更簡單 的方法，以一次操作即可在玻璃基板上設置一定厚之高品 質之介電體層。又，如此方式所形成的介電體層並無介電 特性之偏差而具有適用爲PDP的特性。 本發明之第3狀態，係關於玻璃基板上設置有介電體 層的PDP用構件。本發明之PDP用構件之特徵爲：具備 有玻璃基板，及在該玻璃基板之一個主面上所設置的介電 體層者，而介電體層係由本發明之介電體層用組成物而成 者。介電體層之形成可藉由在玻璃基板上依習用之方法塗 佈介電體層用組成物之分散液，或者，將介電體層用組成 物加工爲裸片者轉印至玻璃板上之後，將此等加以燒成而 實施。雖然並不特別限定，惟介電體層之形成可藉由裸片 之轉印，而按簡便且高效率之方式實施。 以下，就使用裸片以形成設置在PDP之背面玻璃基 板的白色介電體層的情形，加以簡單說明。第2圖係說明 PDP用構件之製作例的過程圖。以下，按照第2圖，就在 玻璃基板上形成白色介電體層的情形，加以說明。 首先，使用刮刀塗佈機或壓模塗佈機，將含有既定成 份的本發明之介電體層用組成物塗佈在剝離薄膜1 〇上面 。接著，使用乾燥機將所塗佈的組成物，在90至130°C 下之溫度進行乾燥，在剝離薄膜10上製得厚度10至 -19- 1296567 (14) 200μιη，較佳爲20至ΙΟΟμιη之具有均勻厚度的裸片12。 接著，在裸片1 2上貼附另一片剝離薄膜1 1。如此方式可 製得按將本發明之介電體層用組成物挾持於剝離薄膜1 〇 及1 1之間的構成使其薄膜化的片狀形成物1 3 (如第2 ( a )圖）。 · 從所得的片狀形成物1 3去除剝離薄膜1 0、1 1，並將 _ 裸片12貼黏在表面形有位址電極4的背面板用玻璃基板 2上（如第2(b)圖）。 φ 接著，將經貼黏在背面板用玻璃基板2的裸片1 2在 燒成爐內加以燒成。燒成時，例如第1階段，在3 00至 450 °C之溫度進行10至60分鐘之暫燒，接著，第2階段 ，在500至700 °C之溫度進行20至90分鐘之本燒成即可 完成。如此方式，即可形成厚度5至ΙΟΟμιη，較佳爲7 至90μπΐ之白色介電體層6(如第2(c)圖）。 如上述方式所得的白色介電體層6，可展現優異的耐 電壓特性。 Φ 另外，在上述說明係就設置在PDP之背面板用玻璃 基板2的白色介電體層6所記載者，惟對將設置在前面板 用玻璃基板1的透通介電體層5(參照第1圖），亦可依 - 同樣方法加以形成。 實施例 以下，藉由實施例，將本發明更具體方式加以說明。 但本發明並不因下述之實施例所限定，當然，不脫離本發 -20- 1296567 (15) 明之主旨的範圍下，可作種種變更。 另外，在各實施例中所調整的組成物之分散狀態以及 有關介電體層之特性的評估方法，係如下所述。 1.有關組成物之分散狀態的評估 介電體層用組成物之分散狀態，係就介電體層用組成 Λ 物中之粗粒中之存在與否、粒度測定機（grinder )値、玻 璃料之沈降情形之檢查而加以評估。 Φ 粗粒子存在與否 對粗粒子存在與否，係按每分散時間或按每放置時間 採取介電體層用組成物，並使用鐵士達產業（股）製之粒 度測定機，以目視確認未發生條紋（cords )的面之狀態 ，列示介電體層用組成物中可確認的粗粒子之狀態。 粒度測定機値 · 對粒度測定機値，係按每分散時間或按每放且時間採 取介電體層用組成物，使用鐵士達產業（股）製之粒度測 定機以測定所分散的粒子之最大粒徑。 . 玻璃料之沈降 使用分散機將組成物處理一定時間後，按每放置時間 採取介電體層用組成物，以目視確認玻璃粒之沈降有無發 生。 -21 - 1296567 (16) 2.介電體層之評估方法 介電體層之評估，係藉由介電體層之耐電壓及介電體 層之表面粗糙度之測定而實施者。 耐電壓 爲測定介電體層之耐電壓，將從介電體層用組成物所 製得的裸片貼黏在附有電極之玻璃基板上，接著，在因燒 成所形成的介電體層上面，再形成評估用之電極以製作耐 電壓測定用試樣。就此耐電壓測定用試樣，使用菊水電子 工業（股）製之耐電壓測定機以測定耐電壓。再者，根據 測定所得之耐電壓之値是否超過〇.5kV以判斷介電體層之 適用性。表中以「〇」表示可適用作爲PDP之介電體層 者，而以「X」表示不能適用者。 表面粗糙度 在附有電極之玻璃基板上，將從介電體層用組成物所 製得的裸片貼黏在玻璃基板上，接著，就由燒成所形成的 介電體層，使用明神工機（股）製之接觸式表面粗糙度計 加以測定其介電體層表面並評估。 以下，利用實施例，就本發明加以說明。 (實施例1 ) -22- 1296567 (17) 將下列所示的各成份裝入分散機，並使用珠磨使其分 散以調製白色介電體層用組成物。在調製中按每分散時間 採取組成物，就其分散狀態按照上述之方法加以評估。 其結果如表1。1296567 • (1) 玖 发明 发明 发明 发明 发明 发明 发明 发明 发明 】 】 】 】 】 】 】 】 】 】 】 】 】 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电(green sheet), and a PDP member having a dielectric layer formed using a die. [Prior Art] A representative image display device is known to use a liquid crystal display, an electroluminescent display, or a plasma display. Among such image display devices, PDPs using plasma display have been attracting attention in recent years, and various performances for improving the quality, low power consumption, thinning, and low price of such devices are being improved. research. Fig. 1 is a schematic cross-sectional view showing an example of a PDP structure. As shown in Fig. 1, the PDP has one of a glass substrate 1 for a front panel and a glass substrate 2 for a back surface which are to be released on the light, and a transparent electrode is formed on each of the inner surfaces of the glass substrates. 3 and address electrodes. The transparent electrode 3 and the address electrode 5 are covered by the transparent dielectric layer 5 and the white dielectric layer 6, respectively, and the transparent dielectric layer 5 is provided with a protective film 7. Between the glass substrate 1 and the substrate 2 configured as described above, a discharge space (pixel) separated by the spacer 8 is formed, and a phosphor 9 is provided for each pixel. For the realization of high-quality PDP, the transparent dielectric layer 5 and the white dielectric layer 6 need to have a uniform thickness, and the surface thereof must be smooth 1296567 • (2). If the uniformity of the dielectric layer and the surface smoothness are insufficient, there is a possibility that the dielectric layer cannot be insulated or the dielectric characteristics are deviated to cause display defects on the PDP. Further, in order to prevent cell defects due to voltage during discharge of the PDP, the dielectric layer needs to have excellent withstand voltage characteristics. The dielectric layer of the PDP generally needs to be resistant to voltages above 0.5 kV. The dielectric layer is formed by providing a coating layer of a dielectric material on a glass substrate, and then firing the coating layer. Therefore, the coating layer provided on the glass substrate needs to be uniform and smooth. An example of a coating method is known as screen printing. When a dielectric layer is formed by a screen printing method, a paste containing a glass frit and a resin is printed on a glass substrate, followed by drying. Finally, the coating layer formed on the glass substrate is fired to form a dielectric layer. However, since the screen printing method is a so-called wet method, the film thickness of the coating layer which can be formed at one time naturally has its limit. Further, in the case of thick coating of the coating layer, it is necessary to repeat the multiple printing of the operation of ejecting the paste after printing the paste and printing the paste. Therefore, not only the work efficiency is poor, but also there is a possibility that a solvent remains in the coating layer. As a result, not only the cost required for coating is high, but also the residual solvent adversely affects the coating layer, and eventually the performance of the dielectric layer is lowered. In view of such a situation, there are reports on several methods in which a dielectric material is previously formed into a sheet shape on a substrate. For example, a method of manufacturing a glazed ceramic substrate in which a glass layer 1296567 (3) is formed on a ceramic substrate is disclosed in Japanese Laid-Open Patent Publication No. SHO 61-226. In this method, a process of forming a dispersion containing a glass frit or a vitrifiable material on a belt or a film to form a die containing a glass frit or a vitrifiable material, And a process of pressing the obtained bare chip on the ceramic substrate, and then heating the film to fuse the die on the ceramic substrate, and forming a glass layer on the ceramic substrate. However, according to this method, there is a problem that the adhesion to the bare substrate of the ceramic substrate is weak. Further, Japanese Laid-Open Patent Publication No. SHO-63-197640 and Japanese Patent Laid-Open No. SHO-64-73086 disclose that a glass frit and a binder are mainly contained, and if necessary, an inorganic powder is added to form a powder sheet. And a coating method of a process of press-bonding a powder sheet onto an object to be coated via a pressure-sensitive adhesive layer, and a process of subsequently firing the obtained laminate. However, according to this method, the manufacturing process will be complicated due to the need to additionally provide a pressure-sensitive adhesive layer. Further, in the case where the pressure-sensitive adhesive component is thermally decomposed during the firing, the glass layer is swollen by the gas generated by the thermal decomposition, so that the quality of the dielectric article is lowered. In order to solve the above problem, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A composition and a method of producing a transparent dielectric layer using a dry film made of such a composition. Further, Japanese Laid-Open Patent Publication No. Hei 9-102273 discloses a film forming material layer formed of a paste-like composition containing a glass powder, a binder resin, and a solvent on the surface of a ceramic substrate, and -9- 1296567 • (4) A method of manufacturing a PDP in which a dielectric layer is formed on the surface of a ceramic substrate by firing the layer. However, in any of the above methods, the composition of the dielectric layer is often processed into a sheet form immediately after the composition for the dielectric layer is prepared, and the composition is still maintained or delivered in a state of being modulated. When the composition is placed for a long time, the dispersibility of the particles contained in the composition is lowered, and in particular, particles having a high specific gravity such as glass frit are likely to undergo secondary aggregation. As a result, the composition having deteriorated dispersion state is processed into a sheet shape, and when such a composition is used to form a dielectric layer, the resulting dielectric layer has many defects, and it is difficult to obtain characteristics required as a dielectric. In view of the above, an object of the present invention is to provide a dielectric layer composition which is excellent in uniformity and smoothness, can be formed with a dielectric layer having excellent withstand voltage characteristics, and can be improved in dispersibility of a glass frit. And a die for a dielectric layer and a member for a PDP which are formed of such a composition. A composition for a dielectric layer of a plasma display panel of the present invention, characterized by comprising a glass frit containing at least a glass component, a dispersing agent, a thermally decomposable binder, and a solvent, and the dispersing agent is a polycarboxylic acid polymer Here, the polycarboxylic acid-based polymer compound is preferably a partial ester selected from the group consisting of an α-olefin/maleic anhydride copolymer, an aliphatic polycarboxylate, and an aliphatic polycarboxylic acid. Alkane group. The content of the above dispersing agent is preferably in the range of from 0.01 to 5.0% by weight based on the total weight of the composition, more preferably -10- 1296567 ‘(5). The above glass frit preferably further contains a ceramic crucible. The maximum particle diameter of the above glass frit is preferably 20 μm or less in a dispersed state. A die for a dielectric layer of a plasma display panel of the present invention is characterized in that the composition for a dielectric layer of the present invention is applied onto a support and then dried. The member for a plasma display of the present invention is characterized by comprising a glass substrate, and a dielectric layer formed of the above-described composition for a dielectric layer of the present invention provided on one main surface of the glass substrate. The objects, effects, features and advantages of the present invention will become apparent from the accompanying drawings. [Embodiment] Hereinafter, the present invention will be described in more detail. The first state of the present invention relates to a composition for forming a PDP dielectric layer. The composition for a dielectric layer of the present invention is characterized by containing a glass frit containing at least a glass component, a thermally decomposable binder, a solvent, and a polycarboxylic acid polymer compound selected as a dispersant. The composition for a dielectric layer of the present invention is characterized in that a polycarboxylic acid-based polymer compound is used as a dispersing agent in order to improve the dispersibility of the glass frit. Here, the term "polycarboxylic acid-based polymer compound" as used in the specification means a partial ester containing an α-olefin/maleic anhydride copolymer, an aliphatic polybasic acid salt, and an aliphatic polyphthalic acid special. In the polyoxan or the like, a polymer compound having a plurality of carboxylic acid groups in the molecule -11 - 1296567 (6) is intended. When the polycarboxylic acid-based polymer compound is compared with a known dispersant such as a decane coupling agent or a general surfactant, particles having a high specific gravity such as a glass frit can be favorably dispersed. In particular, a partial ester of an α-olefin/maleic anhydride copolymer exhibits an excellent dispersion effect. Therefore, when the polycarboxylic acid-based polymer compound is used as a dispersing agent, the dispersibility of the glass frit in the composition for a dielectric layer can be improved to keep the composition in a good dispersion state. That is, the phenomenon in which the glass frit agglomerates to form secondary particles can be suppressed. As a result, variations in the dielectric characteristics of the dielectric layer can be improved, and the withstand voltage of the dielectric layer can be improved. The content of the dispersant is preferably in the range of 0.01 to 5.0% by weight based on the total weight of the composition for the dielectric layer. When the content of the dispersant is at most 0.1% by weight, the glass frit cannot be uniformly dispersed even if the composition is treated by a disperser. Further, when the content of the dispersant exceeds 5% by weight, the dispersant remains in the dielectric layer after firing, which causes a decrease in withstand voltage. The glass frit contained in the composition contains at least a glass component and, if necessary, a ceramic crucible. Here, the term "glass frit" as used in the present specification means the general meaning of the main inorganic components contained in the dielectric layer when the composition is fired to form a dielectric layer. The glass component contained in the glass frit can be generally used as a glass component. For example, Pb〇-β2ο3 (lead oxide boron oxide) glass, Pb0-B203-SiO2 (lead oxide boron oxide monoxide) glass, PbO — b2〇3 — Si〇2 — a1203 (oxidation Lead-Boron Oxide-Oxidation-12-1296567 (7) 矽-Alumina) Glass, ZnO — B2〇3 — Si02 (Zinc Oxide Boron Oxide Oxide) Glass, PbO — ZnO — B2〇3 — Si02 (lead oxide - zinc oxide - boron oxide - cerium oxide) is glass, Na20 - B2 〇 3 - SiO 2 (sodium oxide boron oxide - cerium oxide) glass, BaO - CaO - Si02 (cerium oxide - calcium oxide - cerium oxide A glass or the like is preferably a PbO-b2o3-si〇2-ai2o3 glass. More specifically, the glass component of the glass frit is preferably from 30 to 75% by weight of PbO, and from 1 to 40% by weight of B2O3, and from 1 to 40% by weight of Si〇2, and from 1 to 10% by weight of Al2. 〇3 is formed. As an example of good use, a glass component composed of 60% by weight of PbO, 10% by weight of B2〇3, and 25% by weight of SiO 2 , and 5% by weight of ai 2 o 3 may be mentioned. The particle size of the glass component is not particularly limited. However, in the preparation of the composition, the average particle diameter of the glass component which is preferably used in the present invention is in the range of 0.5 to 5 μm in order to achieve a good dispersion state. When a white dielectric layer provided on the back side of the PDP is formed, as a glass frit, a ceramic tantalum component is added in addition to the glass component. Examples of the ceramic tantalum component which can be used in the present invention include TiO 2 (titanium oxide), Al 2 〇 3 (alumina), SiO 2 (yttria), and ZrO 2 (yttrium). Although not particularly limited, it is preferably Ti〇2 and ai2o3. The particle size of the dip material is not particularly limited. However, in order to achieve a good dispersion state in the preparation of the composition, the ceramic crumb component which is preferably used in the present invention has an average particle diameter in the range of 〇·1 to 5 μm. The ratio of the glass component to the ceramic tantalum component in the glass frit is based on the total weight of the glass component of 50 to 1 Torr. /. And the ceramic material has a composition of 50% by weight. Preferably, in the case of the composition of the back (white) dielectric -13 - 1296567 (8) layer, the glass composition is 50 to 90% by weight and the ceramic composition is 50 to 10% by weight. Further, in the case of the front (transparent) dielectric layer composition, it is preferred that the glass component has a weight of 1 〇. /. And the pottery ingredients are 〇% by weight. The glass frit may be contained in the range of 40 to 80% by weight based on the total weight of the composition. The thermally decomposable binder used in the present invention is one in which a composition for a dielectric layer is bonded to a glass substrate. Although it is not particularly limited, an acrylic resin is exemplified as an example of a good thermal decomposition adhesive. The acryl resin may include a copolymer of a (meth) acrylate compound, a copolymer of two or more kinds of (meth) acrylate compounds, and a copolymer of a (meth) acrylate compound and another copolymerizable monomer. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate. Butyl methacrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate Ester, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (methyl) Ethylhexyl acrylate, decyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecane (meth) acrylate An alkyl (meth)acrylate such as an ester, lauryl (meth)acrylate, stearyl (meth)acrylate or isostearyl (meth)acrylate; hydroxyethyl (meth)acrylate; 2-hydroxypropyl methacrylate, (methyl-14-1296567 (9) yl) (meth)acrylic acid hydroxy group such as 4-hydroxybutyl acrylate, 3-hydroxypropyl (meth) acrylate, (2-) hydroxybutyl 2-(hydroxy) acrylate, 3-hydroxybutyl (meth) acrylate An alkyl group; a phenoxyalkyl (meth)acrylate such as (meth)acrylic acid phenoxyethyl ester; (meth)acrylic acid 2-hydroxy-3-phenoxypropyl ester; (meth)acrylic acid 2 - Methoxyethyl ester, 2-ethoxyethyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, (meth)acrylic acid (A) alkoxyalkyl (meth)acrylate such as 2-methoxybutyl ester; polyethylene glycol mono (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, methoxy polymerization Ethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, Methoxy polypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (methyl) propyl a polyalkylene glycol (meth) acrylate such as an enoate; a cyclohexyl (meth) acrylate, a 4-butylcyclohexyl (meth) acrylate, a dicyclopentanyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, borneol (meth) acrylate, isobornyl (meth) acrylate, tricyclodecyl ( A cycloalkyl (meth) acrylate such as a methyl acrylate; a benzyl (meth) acrylate or a tetrahydrofuran (meth) acrylate. Among them, an alkyl (meth)acrylate or an alkoxyalkyl (meth)acrylate is preferred, and a particularly preferred (meth)acrylate is (methyl-15-1296567 (10)). Butyl phthalate, ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and (meth)acrylic acid 2-ethyl ethyl ester. The other copolymer monomer is not particularly limited as long as it is a compound copolymerizable with the above (meth) acrylate compound, and examples thereof include (meth)acrylic acid, vinyl benzoic acid, and maleic acid. Unsaturated carboxylic acids such as vinyl phthalic acid; vinyl benzyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, butadiene, isoprene, etc. Polymeric compound. The content of the thermally decomposable binder is not particularly limited, but is preferably in the range of 5 to 30% by weight based on the total weight of the composition for the dielectric layer. The solvent to be used in the present invention is preferably one which imparts appropriate fluidity or plasticity to a composition for a dielectric layer and has good film formability. The solvent which can be used may, for example, be an ether, an ester, an ether ester, a ketone, a ketone ester, a guanamine, a guanamine ester, an indoleamine, a lactone, or a sub Codes, codes, hydrocarbons, halogenated hydrocarbons, etc. Specific examples of preferred solvents include: toluene, ethyl acetate, and methyl ethyl ketone. The above solvents may be used singly or in combination of two or more. The content of the solvent is in the range of 15 to 55 wt% based on the total weight of the composition for the dielectric layer. In the present invention, the composition for the dielectric layer may be further contained as an additive: Addition of a plasticizer such as a diester-based plasticizer, a bonding agent, a storage stabilizer, an antifoaming agent, a thermal decomposition accelerator, and an antioxidant, etc. - 16- 1296567 (11). These additives are not particularly limited, and those which are commonly used in the field can be appropriately selected. Although it is not particularly limited, a preferred embodiment of the composition for a dielectric layer of the present invention contains: a glass component containing Pb0/B203/SiO2/Al203 = 60/1 0/25/5 wt% and Al203. / Ti02 ceramic frit component frit, and 2-ethylhexyl acrylate (thermal decomposable binder), and partial ester (dispersant) of α-olefin/maleic anhydride copolymer, and adipic acid Dibutyl ester (plasticizer), and a composition of toluene (solvent). Further, another preferred embodiment of the composition for a dielectric layer of the present invention contains a glass frit containing a glass component of PbO/B2O3/SiO2/Al2O3 = 60/1 0/25/5% by weight, and 2-ethylhexyl acrylate (thermal decomposable binder), and partial ester (dispersant) of α-olefin/maleic anhydride copolymer, and dibutyl adipate (plasticizer), and toluene (solvent) The composition of ). In the composition for a dielectric layer of the present invention, a glass frit, a dispersant, a thermally decomposable binder, and various additives added as necessary are premixed with a solvent, and for example, a ball mill, a bead mill, or a three-roll mill can be used. A disperser such as a mill, a kneader or the like is mechanically dispersed to prepare. In order to make the dispersion state of the composition more uniform, it is also possible to extend the processing time of the dispersing machine or to select a dispersing machine which is more effectively dispersed. In the glass frit in a dispersed state, the primary particles are uniformly dispersed by the excellent dispersing action of the polycarboxylic acid-based polymer compound, and secondary aggregation can be suppressed. The maximum particle diameter of the glass frit is preferably 20 μm or less in the dispersed state. If the maximum particle size of the glass frit exceeds 20 μm, the dielectric layer of the composition -17-1296567 (12) will easily cause defects such as pinholes on the surface, making it difficult to obtain the required Withstand voltage characteristics. As described above, since the composition for a dielectric layer of the present invention is a dispersant, a polycarboxylic acid-based polymer compound is used, and the dispersion state of the glass frit can be appropriately adjusted to achieve a good dispersion state. Further, since the polycondensation of the polycarboxylic acid-based polymer compound can prevent secondary aggregation of the glass frit, it is possible to maintain a good dispersion state for a long period of time when the composition is prepared. Therefore, by using the composition for a dielectric layer of the present invention, a dielectric layer excellent in withstand voltage and dielectric characteristics can be formed. The second state of the present invention relates to a die used for forming a dielectric layer of P D P . The die of the present invention is characterized in that the composition for a dielectric layer of the present invention described above is coated on a support and then dried. The die of the present invention, more specifically, a composition containing at least a glass frit, a polycarboxylic acid-based polymer compound, a thermally decomposable binder, and a solvent, is sufficiently mixed to uniformly disperse the glass frit, and is coated by a doctor blade. The obtained dispersion liquid is applied to a support such as a polyethylene terephthalate film by a method such as a cloth method or a die coating method, and is dried to remove a solvent to form a film. The die on the support has adhesiveness and is excellent in flexibility, workability, and handleability, and can be easily transferred onto a glass substrate. Here, "having adhesiveness" means that when a bare die is in contact with a glass substrate at room temperature or under heating, the bare chip is adhered to the glass substrate and fixed. Here, in order to improve the peelability when the bare board is transferred onto the glass substrate, the -18-1296567 (13) support is preferably a surface treatment agent such as polysiloxane. The bare board transferred to the glass substrate is fired to form a dielectric layer containing a glass component as a main component. Since the above die is used to form the dielectric layer, a relatively high-quality dielectric layer can be provided on the glass substrate in a single operation by a simple method. Further, the dielectric layer formed in this manner has a characteristic of being applied as a PDP without variation in dielectric characteristics. The third aspect of the present invention relates to a member for a PDP in which a dielectric layer is provided on a glass substrate. The member for PDP of the present invention is characterized in that it has a glass substrate and a dielectric layer provided on one main surface of the glass substrate, and the dielectric layer is composed of a composition for a dielectric layer of the present invention. . The formation of the dielectric layer may be performed by applying a dispersion of the composition for a dielectric layer on a glass substrate, or by transferring the composition of the dielectric layer into a die and transferring it to a glass plate. This is carried out by firing. Although not particularly limited, the formation of the dielectric layer can be carried out in a simple and efficient manner by transfer of the die. Hereinafter, a case where a bare chip is used to form a white dielectric layer provided on the back glass substrate of the PDP will be briefly described. Fig. 2 is a process diagram for explaining a production example of a member for PDP. Hereinafter, a case where a white dielectric layer is formed on a glass substrate will be described with reference to Fig. 2 . First, a composition for a dielectric layer of the present invention containing a predetermined component is applied onto a release film 1 使用 using a knife coater or a die coater. Next, the applied composition is dried at a temperature of 90 to 130 ° C using a dryer to obtain a thickness of 10 to -19 to 1296567 (14) 200 μmη, preferably 20 to ΙΟΟμιη, on the release film 10. A die 12 having a uniform thickness. Next, another release film 11 is attached to the die 12. In this manner, a sheet-like formation 13 having a structure in which the composition for a dielectric layer of the present invention is held between the release film 1 〇 and 1 1 can be obtained (as shown in Fig. 2 (a)). - The release film 10, 1 1 is removed from the obtained sheet-like formation 1 3, and the _ die 12 is adhered to the glass substrate 2 for a back surface having the address electrode 4 (for example, the second (b) Figure). φ Next, the bare sheet 12 adhered to the glass substrate 2 for back sheet is fired in a firing furnace. In the case of firing, for example, the first stage is carried out at a temperature of 300 to 450 ° C for 10 to 60 minutes, and then, in the second stage, at a temperature of 500 to 700 ° C for 20 to 90 minutes. It can be done. In this manner, a white dielectric layer 6 having a thickness of 5 to ΙΟΟμηη, preferably 7 to 90 μπΐ, can be formed (as shown in Fig. 2(c)). The white dielectric layer 6 obtained as described above can exhibit excellent withstand voltage characteristics. Φ In addition, the above description is described in the white dielectric layer 6 of the glass substrate 2 for a back panel of the PDP, but the dielectric layer 5 to be provided on the glass substrate 1 for the front panel (see the first Figure) can also be formed in the same way. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited by the following examples, and various modifications can be made without departing from the spirit and scope of the invention. Further, the dispersion state of the composition to be adjusted in each of the examples and the evaluation method of the characteristics of the dielectric layer are as follows. 1. Evaluation of the dispersion state of the composition The dispersion state of the composition for the dielectric layer is the presence or absence of the coarse particles in the composition of the dielectric layer, the grinder, the frit The inspection of the settlement situation is evaluated. Φ The presence or absence of coarse particles for the presence or absence of coarse particles, the composition for the dielectric layer is taken for each dispersion time or for each set time, and the particle size measuring machine manufactured by Tiesida Industries Co., Ltd. is used to visually confirm The state of the surface where the stripes are generated, and the state of the coarse particles which can be confirmed in the composition for the dielectric layer is listed. Particle size measuring machine 对 For the particle size measuring machine, a composition for a dielectric layer is used for each dispersion time or for each discharge time, and a particle size measuring machine manufactured by Tiesida Industries Co., Ltd. is used to measure the dispersed particles. Maximum particle size. . Settling of the glass frit After the composition was treated with a dispersing machine for a certain period of time, the composition for the dielectric layer was taken for each standing time to visually confirm the presence or absence of sedimentation of the glass particles. -21 - 1296567 (16) 2. Evaluation method of dielectric layer The evaluation of the dielectric layer was carried out by measuring the withstand voltage of the dielectric layer and the surface roughness of the dielectric layer. The withstand voltage is a measurement of the withstand voltage of the dielectric layer, and the die obtained from the composition for the dielectric layer is adhered to the glass substrate with the electrode, and then, on the dielectric layer formed by firing, Further, an electrode for evaluation was formed to prepare a sample for voltage withstand measurement. For the withstand voltage measurement sample, a withstand voltage measuring machine manufactured by Kikusui Electronics Co., Ltd. was used to measure the withstand voltage. Further, the applicability of the dielectric layer was judged based on whether or not the measured withstand voltage was more than 〇5 kV. In the table, "〇" indicates that it can be applied as a dielectric layer of a PDP, and "X" indicates that it cannot be applied. The surface roughness is adhered to the glass substrate on the glass substrate with the electrode, and the die obtained from the composition for the dielectric layer is adhered to the glass substrate, and then the dielectric layer formed by firing is used. A contact surface roughness meter made of (strand) was used to measure the surface of the dielectric layer and evaluate it. Hereinafter, the present invention will be described by way of examples. (Example 1) -22- 1296567 (17) The components shown below were placed in a disperser and dispersed by a bead mill to prepare a composition for a white dielectric layer. The composition was taken at a time of dispersion in the preparation, and its dispersion state was evaluated in accordance with the above method. The results are shown in Table 1.
-23- 1296567 (18) 成份 重量份 玻璃料 玻璃成份 65重量％ (Pb0/B203/Si02/Al203 = 60/10 / 25/5 重量 ％， 平均粒徑1·〇μιη，最大粒徑20μιη) 陶瓷塡料成份 3 5重量％ (Ti02/Al203 = 43/57 重量。/〇 ) 100 熱分解性黏合劑 2-乙基己基丙烯酸酯 40 分散劑 α -烯烴/馬來酸酐共聚物之部分酯 (弗洛連G-700 (商品名，共榮社化學（股）製） 0.3 可塑劑 己二酸二丁酯 (東洋油墨製造（股）製） 0.8 溶劑 甲苯 50-23- 1296567 (18) Component weight parts glass frit glass composition 65 wt% (Pb0/B203/SiO2/Al203 = 60/10 / 25/5 wt%, average particle size 1·〇μιη, maximum particle size 20μιη) Ceramics Dipping component 35 wt% (Ti02/Al203 = 43/57 wt./〇) 100 Thermally decomposable binder 2-ethylhexyl acrylate 40 Dispersant Partial ester of α-olefin/maleic anhydride copolymer Luolian G-700 (trade name, Gongrongshe Chemical Co., Ltd.) 0.3 Plasticizer Dibutyl adipate (made by Toyo Ink Co., Ltd.) 0.8 Solvent Toluene 50
接著，使用所得的各組成物，按下述步驟在玻璃基板 上製作白色介電體層。首先，在經以聚矽氧烷樹脂施予剝 離處理之厚度38μιη之聚對苯二甲酸乙二醇酯製剝離薄膜 上，使用刮刀塗佈機將先前所調製之各組成物加以塗佈。 接著，使用乾燥機在100°C下乾燥2分鐘所得的塗膜，以 -24- 1296567 ，(19) 形成均勻的膜厚50μιη之裸片。接著’將剝離薄膜上之裸 片貼黏在附有電極之玻璃基板上之後，從裸片去除剝離薄 膜。其次，將貼黏有裸片的玻璃基板在400°C下燒成20 分鐘，接著按每分鐘l〇°C之速度升溫至5 80°C，並在580 °C燒成40分鐘以製得厚度20μιη之白色介電體層。按照 先前所說明之方法，測定所得的介電體層之耐電壓及表面 粗糙度。其結果如表1。 (實施例2 ) 將如下列所示的各成份裝入分散機，並使用珠磨使其 分散1 6小時以調製透明介電體層用組成物。就所得的組 成物之分散狀態按照先前所說明的方法加以評估。其結果 如表1。 -25- 1296567 .(20) 成份 重量份 玻璃料 玻璃成份 1 〇 〇重量％ (Pb0/B203/Si02/Al203 = 60/1 0 / 25/5 重量％， 平均粒徑1·5μιη，最大粒徑18μιη) 100 熱分解性黏合劑 聚2-乙基己基丙烯酸酯 15 分散劑 α -烯烴/馬來酸酐共聚物之部分酯 (弗洛連G-700 (商品名，共榮社化學（股）製） 0.3 可塑劑 己二酸二丁酯 (東洋油墨製造（股）製） 4.5 溶劑 甲苯 35Next, using the obtained composition, a white dielectric layer was formed on the glass substrate in the following procedure. First, each of the previously prepared compositions was coated on a polyethylene terephthalate release film having a thickness of 38 μm by a stripping treatment with a polyoxyalkylene resin. Next, the resulting coating film was dried at 100 ° C for 2 minutes using a dryer to form a uniform film having a film thickness of 50 μm at -24 to 1296567 (19). Next, after the bare film on the release film is adhered to the glass substrate with the electrode attached, the release film is removed from the die. Next, the glass substrate adhered to the die was fired at 400 ° C for 20 minutes, then heated to 580 ° C at a rate of 10 ° C per minute, and fired at 580 ° C for 40 minutes to obtain. A white dielectric layer having a thickness of 20 μm. The withstand voltage and surface roughness of the resulting dielectric layer were measured in accordance with the method described previously. The results are shown in Table 1. (Example 2) Each component as shown below was placed in a disperser and dispersed by a bead mill for 16 hours to prepare a composition for a transparent dielectric layer. The dispersion state of the obtained composition was evaluated in accordance with the method described previously. The results are shown in Table 1. -25- 1296567 .(20) Component parts by weight glass frit component 1 〇〇% by weight (Pb0/B203/SiO2/Al203 = 60/1 0 / 25/5 wt%, average particle size 1. 5 μιη, maximum particle size 18μιη) 100 Thermally decomposable adhesive Polyethyl 2-ethylhexyl acrylate 15 Dispersant Partial ester of α-olefin/maleic anhydride copolymer (Florin G-700 (trade name, Kyoeisha Chemical Co., Ltd.) 0.3 Plasticizer Dibutyl Adipate (made by Toyo Ink Manufacturing Co., Ltd.) 4.5 Solvent Toluene 35
接著，使用所得的組成物，按下述步驟在玻璃基板上 製作透明介電體層。首先，在以聚矽氧烷樹脂施予剝離處 理厚度38μιη之聚對苯二甲酸乙二醇酯製剝離薄膜上，使 用刮刀塗佈機將先前所調製之組成物加以塗佈。接著，使 用乾燥機在1〇〇 °C下乾燥2分鐘所得的塗膜，以形成均勻 的膜厚65 μιη之裸片。接著，將剝離薄膜上之裸片貼黏在 附有電極之玻璃基板上之後，從裸片去除剝離薄膜。其次 -26- (21) 1296567 ，將貼黏有裸片的玻璃基板在420°C下燒成 著按每分鐘l〇°C之速度升溫至620°C，並在 分鐘以製得厚度約30μιη之透明介電體層。 明之評估方法，測定所得的介電體層之耐電 度。其結果如表1。 (比較例1 ) 除不含有分散劑以外，調製由與實施例 成的白色介電體層用組成物，並就其分散狀 說明的方法加以評估。其結果如表1。 其次，按與實施例1同樣方式將所得的 化，並繼續進行燒成藉以在玻璃基板上形成 。就所得的介電體層，按照先前所說明的方 及表面粗糙度。其結果如表1。 (比較例2 ) 除將作爲分散劑所使用的α -烯烴/馬 之部份酯之量作成〇·〇1重量份以外，其他 例1同樣成份而成的白色介電體層用組成物 狀態按照先前所說明的方法加以評估。在此 使分散時間爲1 6小時的組成物，其結果如_ 其次，按與實施例1同樣方式將所得的 ，並繼續進行燒成藉以在玻璃基板上形成白 就所得的介電體層，按照先前所說明的方法 20分鐘，接 6 2 0 °C 燒成 6 0 按照先前所說 壓及表面粗糙 1同樣成份而 態按照先前所 各組成物裸片 白色介電體層 法測定耐電壓 來酸酐共聚物 則調製與實施 ，並就其分散 ，評估則使用 i 1 ° 組成物裸片化 色介電體層。 測定耐電壓及 -27- 1296567 ，(22) 表面粗糙度。其結果如表1。 (比較例3 ) 除將作爲分散劑所使用的α 一烯烴/馬來酸酐共聚物 之部份酯之量作成1 0重量份以外，其他則調製與實施例 1同樣成份而成的白色介電體層用組成物，並就其分散狀 態按照先前所說明的方法加以評估。在此，評估則使用使 分散時間爲1 6小時的組成物，其結果如表1。 其次’按與實施例1同樣方式將所得的組成物裸片化 ’並繼續進行燒成藉以在玻璃基板上形成白色介電體層。 就所得的介電體層，按照先前所說明的方法測定耐電壓及 表面粗糙度。其結果如表1。 (實施例3 ) 除作爲分散劑係使用脂肪族聚羧酸鈉（弗洛連G -6〇〇，共榮社化學（股）製）1〇重量份以外，其餘則與實 施例1同樣方式調製白色介電體層用組成物。就使分散時 間爲1 6小時的組成物，按照先前所說明的方法評估其分 散狀態。其結果如表1。 其次’按與實施例1同樣方式將所得的組成物裸片化 ’並繼續進行燒成藉以在玻璃基板上形成白色介電體層。 就所得的介電體層，按照先前所說明的方法測定耐電壓及 表面粗糙度。其結果如表1。 -28- 1296567 (23) (實施例4 ) 除分散劑係使用脂肪族聚羧酸特殊聚矽氧烷（弗洛連 AF — 1 005，共榮社化學（股）製）1.〇重量份以外，其餘 則與實施例1同樣方式調製白色介電體層用組成物。就使 分散時間爲1 6小時的組成物，按照先前所說明的方法評 估其分散狀態。其結果如表1。 其次，按與實施例1同樣方式將所得的組成物裸片化 ，並繼續進行燒成藉以在玻璃基板上形成白色介電體層。 就所得的介電體層，按照先前所說明的方法測定耐電壓及 表面粗糙度。其結果如表1。 (比較例4 ) 除分散劑係使用油酸1.0重量份以外，其餘則與實施 例1同樣方式調製白色介電體層用組成物。就使分散時間 爲1 6小時的組成物，按照先前所說明的方法評估其分散 狀態。其結果如表1。 其次，按與實施例1同樣方式將所得的組成物裸片化 ，並繼續進行燒成藉以在玻璃基板上形成白色介電體層。 就所得的白色介電體層，按照先前所說明的方法測定耐電 壓及表面粗糙度。其結果如表1。 -29- 1296567Next, using the obtained composition, a transparent dielectric layer was formed on the glass substrate in the following procedure. First, a previously prepared composition was applied onto a polyethylene terephthalate release film having a thickness of 38 μm by a release treatment using a polyoxyalkylene resin. Next, the resulting coating film was dried at 1 ° C for 2 minutes using a dryer to form a uniform film having a film thickness of 65 μm. Next, after the bare chip on the release film is adhered to the glass substrate with the electrode attached, the release film is removed from the die. Next, -26-(21) 1296567, the glass substrate adhered to the die is fired at 420 ° C, and the temperature is raised to 620 ° C at a rate of 10 ° C per minute, and the thickness is about 30 μm in minutes. Transparent dielectric layer. The evaluation method of the present invention measures the resistance of the obtained dielectric layer. The results are shown in Table 1. (Comparative Example 1) A composition for a white dielectric layer formed in the same manner as in the Example was prepared except that the dispersant was not contained, and the method described for the dispersion was evaluated. The results are shown in Table 1. Next, the obtained layer was formed in the same manner as in Example 1 and continued to be fired to form on a glass substrate. With respect to the resulting dielectric layer, the square and surface roughness as previously described were followed. The results are shown in Table 1. (Comparative Example 2) The state of the composition for a white dielectric layer of the same composition as in Example 1 except that the amount of the α-olefin/horse partial ester used as the dispersing agent was 〇·〇1 part by weight. The method described previously was evaluated. Here, the composition having a dispersion time of 16 hours was used, and the result was as follows. Next, the obtained dielectric layer was formed in the same manner as in Example 1 and then burned to form white on a glass substrate. The previously described method was carried out for 20 minutes, followed by firing at 60 ° C for 60 ° according to the same composition as previously described, and the same composition of the surface roughness 1 according to the previous composition of the bare white dielectric layer method to determine the withstand voltage to the anhydride copolymerization The material is modulated and implemented, and for its dispersion, the evaluation uses the i 1 ° composition to dilute the dielectric layer. Determine the withstand voltage and -27- 1296567, (22) surface roughness. The results are shown in Table 1. (Comparative Example 3) A white dielectric having the same composition as that of Example 1 except that the amount of the partial ester of the α-olefin/maleic anhydride copolymer used as the dispersing agent was made 10 parts by weight. The bulk layer was evaluated using the composition and its dispersion state as previously described. Here, the evaluation was carried out using a composition having a dispersion time of 16 hours, and the results are shown in Table 1. Next, the obtained composition was diced in the same manner as in Example 1 and the firing was continued to form a white dielectric layer on the glass substrate. With respect to the obtained dielectric layer, the withstand voltage and surface roughness were measured in accordance with the method described previously. The results are shown in Table 1. (Example 3) The same procedure as in Example 1 was carried out, except that 1 part by weight of an aliphatic polycarboxylate (Florin G -6 〇〇, manufactured by Kyoeisha Chemical Co., Ltd.) was used as a dispersant. A composition for a white dielectric layer is prepared. The composition was allowed to have a dispersion time of 16 hours, and its dispersion state was evaluated in accordance with the method previously described. The results are shown in Table 1. Next, the obtained composition was diced in the same manner as in Example 1 and the firing was continued to form a white dielectric layer on the glass substrate. With respect to the obtained dielectric layer, the withstand voltage and surface roughness were measured in accordance with the method described previously. The results are shown in Table 1. -28- 1296567 (23) (Example 4) In addition to the dispersant, an aliphatic polycarboxylic acid special polyoxyalkylene (Florin AF-1 005, manufactured by Kyoeisha Chemical Co., Ltd.) was used. The composition for a white dielectric layer was prepared in the same manner as in Example 1 except for the rest. The composition was dispersed for a period of 16 hours, and its dispersion state was evaluated in accordance with the method described previously. The results are shown in Table 1. Next, the obtained composition was diced in the same manner as in Example 1 and the firing was continued to form a white dielectric layer on the glass substrate. With respect to the obtained dielectric layer, the withstand voltage and surface roughness were measured in accordance with the method described previously. The results are shown in Table 1. (Comparative Example 4) A composition for a white dielectric layer was prepared in the same manner as in Example 1 except that 1.0 part by weight of oleic acid was used as the dispersant. The composition was dispersed for a period of 16 hours, and its dispersion state was evaluated in accordance with the method described previously. The results are shown in Table 1. Next, the obtained composition was diced in the same manner as in Example 1 and the firing was continued to form a white dielectric layer on the glass substrate. With respect to the obtained white dielectric layer, the withstand voltage and surface roughness were measured in accordance with the method described previously. The results are shown in Table 1. -29- 1296567
(24) 表面粗糙度 Ra(p m ) (N Ό 〇 〇 〇 d in d s d 00 d (N c5 卜 卜 d> d m d Ό c5 § d 對介電體層之 適用性 X 〇 〇 〇 〇 〇 X X X X 〇 〇 X 耐電壓 (kV) 〇 ^Γϊ Ο 〇 〇 ο 00 r-H <Ν c5 m c> 〇\ m 〇 (N (N d in oo O ο ο 粒度測定 |機値(μ m ) 1 25以上 ^Τ) (Ν 〇 m o uS 25以上 25以上 25以上 in od ο 1 25以上i 1粗粒有無存在 1__ 1相當多 少於4小時 少於8小時 壊 壊 壊 相當多 相當多 相當多 壊 壊 壊 珠磨分散時間 4小時 8小時 12小時 1 14小時 i 16小時 16小時 4小時 16小時 16小時 16小時 16小時 16小時 16小時 分散劑含量 (重量份） m 〇 cn d 〇 r-H 〇 d ο p 〇· 〇 τ-Η 分散劑 弗洛連 G-700a) 挪％ 杂0 壊 弗洛連 G-700a) 弗洛連 G-700a) 弗洛連 G-700a) 弗洛連 AF-1005C) 油酸 實施例號碼 實施例1 實施例2 比較例1 比較例2 比較例3 實施例3 ! ί 實施例4 ； 比較例4 iliill - ο —ii - ^ 謹ii瀣 i 裝 ls(cd -30- 1296567 (25) 由表1可知，如將規定量之聚羧酸系高分子化合物作 爲分散劑使用時，組成物將呈現優異的分散狀態，且從這 種組成物所形成的介電體層則具有優異的特性爲自明（參 照實施例1至4)。又，即使作爲分散劑而使用聚羧酸系 高分子化合物時，如其含量不恰當，仍難於獲得組成物之 良好的分散狀態或難於達成所需要的耐電壓特性爲自明（ 參照比較例2及3 )。另外，隨著分散時間之增加而最大 粒徑在減少者，係表示經凝聚的粒子已被解除凝聚而分散 性已獲改善之意。 另一方面，在組成物中不存在分散劑的比較例1中， 並未能成爲良好的分散狀態。又，即使延長分散時間，其 分散性仍不獲改善，玻璃料引起二次凝聚而使最大粒徑値 增大，且耐電壓特性會降低爲自明。再者，由比較例4可 知，在分子內所存在的羧酸基爲1個之油酸中，其分散效 果不足。 (實施例5) 將在實施例1所調製之分散時間爲1 6小時之組成物 ，在23°C、5 0%RH (相對濕度）之條件下放置，並確認 經過既定時間後之玻璃料之沈降情形。其結果如表2。 (比較例5) 將在比較例1所調製之分散時間爲1 6小時之組成物 ，在23°C、50%RH之條件下放置，並確認經過既定時間 -31 - 1296567 (26) 後之玻璃料之沈降情形。其結果如袠2。 (比較例6) 將在比較例2所調製之分散時間爲1 6小時之組成物 ’在23°C、50%RH之條件下放置，並確認經過既定時間 後玻璃料之沈降情形。其結果如表2。 (比較例7 ) 將在比較例4調製之分散時間爲丨6小時之組成物在 23°C，50°/〇RH之條件下放置，並確認經過既定時間後玻 璃料之沈降情形，其結果如表2。 表 2(24) Surface roughness Ra(pm) (N Ό 〇〇〇d in dsd 00 d (N c5 Bub d> dmd Ό c5 § d Applicability to dielectric layer X 〇〇〇〇〇XXXX 〇〇X Withstand voltage (kV) 〇^Γϊ Ο 〇〇ο 00 rH <Ν c5 m c> 〇\ m 〇(N (N d in oo O ο ο particle size measurement | machine 値 (μ m ) 1 25 or more ^ Τ) (Ν 〇mo uS 25 or more 25 or more 25 in od ο 1 25 or more i 1 coarse grain presence or absence 1__ 1 quite a little less than 8 hours in 4 hours 壊壊壊 quite a considerable amount of 壊壊壊 beads grinding dispersion time 4 hours 8 hours 12 hours 1 14 hours i 16 hours 16 hours 4 hours 16 hours 16 hours 16 hours 16 hours 16 hours 16 hours dispersant content (parts by weight) m 〇cn d 〇rH 〇d ο p 〇· 〇τ-分散 Dispersant Florin G-700a) %% Miscellaneous 壊Florin G-700a) Florian G-700a) Florian G-700a) Florian AF-1005C) Oleic Acid Example Number Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 3 ! ί Example 4 ; Comparative Example 4 iliill - ο - ii - ^ 瀣 瀣 装 cd (cd -30- 1296567 (25) As is apparent from Table 1, when a predetermined amount of a polycarboxylic acid-based polymer compound is used as a dispersing agent, the composition exhibits an excellent dispersion state, and the dielectric layer formed from such a composition has In addition, when a polycarboxylic acid type polymer compound is used as a dispersing agent, if the content is not appropriate, it is difficult to obtain a good dispersion state of the composition or it is difficult to achieve a solution. The required withstand voltage characteristics are self-explanatory (refer to Comparative Examples 2 and 3). In addition, as the maximum particle size decreases as the dispersion time increases, it means that the agglomerated particles have been deagglomerated and the dispersibility has been improved. On the other hand, in Comparative Example 1 in which no dispersant was present in the composition, it did not become in a good dispersion state. Further, even if the dispersion time was prolonged, the dispersibility was not improved, and the glass frit caused secondary aggregation. The maximum particle diameter 値 is increased, and the withstand voltage characteristic is reduced to self-explanatory. Further, as compared with Comparative Example 4, the dispersion effect is obtained by using one oleic acid in the carboxylic acid group present in the molecule. (Example 5) A composition having a dispersion time of 16 hours prepared in Example 1 was placed under conditions of 23 ° C and 50% RH (relative humidity), and it was confirmed that after a predetermined period of time. The settlement of the glass frit. The results are shown in Table 2. (Comparative Example 5) A composition having a dispersion time of Comparative Example 1 of 16 hours was placed under the conditions of 23 ° C and 50% RH, and it was confirmed that the predetermined time -31 - 1296567 (26) was passed. The settlement of the glass frit. The result is as follows. (Comparative Example 6) The composition of the dispersion time of Comparative Example 2, which was set to have a dispersion time of 16 hours, was placed under the conditions of 23 ° C and 50% RH, and the sedimentation of the glass frit after a predetermined period of time was confirmed. The results are shown in Table 2. (Comparative Example 7) The composition having a dispersion time of 丨6 hours prepared in Comparative Example 4 was placed under conditions of 23 ° C and 50 ° / RH, and the sedimentation of the glass frit after a predetermined period of time was confirmed. As shown in Table 2. Table 2
實施例 號碼 放置 時間 沈 降 粗粒有無 存在 粒度測 定機値 (μπι ) 耐電壓 (kV ) 適用 性 實施例 剛分散後 4πτ ιΤΠτ j\\\ 幾乎無 7.5 0.95 〇 5 2星期後 Μ 川、 幾乎無 7.5 0.95 〇 4星期後 jfrrr 無 幾乎無 7.5 0.95 〇 比較例 剛分散後 >fnT Μ 相當多 25以上 0.35 X 5 2星期後 有 相當多 25以上 不能測定* X 比較例 剛分散後 Μ 相當多 25以上 0.39 X 6 2星期後 有 相當多 25以上 不能測定* X 比較例 剛分散後 >fmr Μ 多 25以上 0.44 X 7 2星期後 有 相當多 25以上 0.38 X *未能成膜者。 -32- (27) 1296567 由表2可知，在含有規定量之聚羧酸系高分子化合物 的實施例5中，能長期維持良好的分散狀態。其結果，即 使使用放置4星期的組成物以形成介電體層時，玻璃料之 最大粒徑之値仍然在容許範圍內（20μιη以下），而所形 成的介電體層維持有高的耐電壓特性。 相對於此，可知在組成物中不存在分散劑的比較例5 中，由於玻璃料會引起二次凝聚之故，耐電壓會降低爲自 明。又，如比較例6所示，可知即使作爲分散劑而使用聚 羧酸系高分子化合物時，如其含量不足，即難於維持組成 物之良好的分散狀態爲自明。再者，由比較例7可知，在 分子內所存在的羧酸基爲1個之油酸的情形，其分散效果 不足爲自明。另外，雖將經確認有玻璃料之沈降的，放置 2星期後之介電體層用組成物分別再度攪拌，惟各組成物 均未能恢復剛分散後之狀態。 如上所說明，如採用本發明，而在爲形成介電體層之 組成物中含有能提高如玻璃料等之高比重之粒子之分散性 的聚羧酸系高分子化合物，即能有效改善組成物中之玻璃 料之分散狀態。因而，能以優異的分散狀態調製組成物， 且因可抑制所得分散液之二次凝聚之故，即使保存長時間 後仍然不會發生沈降而能維持良好的分散狀態。 又，如將本發明之介電體層用組成物裸片化，並貼黏 在玻璃基板上，加以燒成，即能容易在玻璃基板上形成具 有所需要的耐電壓特性的介電體層。 -33- 1296567 (28) 再者，如將具備有使用本發明之介電體組成物所形成 之耐電壓特性優異的介電體層之玻璃基板作爲PDP用構 件使用，即能實現在PDP使用時之電漿放電電壓具有耐 性，且單元缺陷少的高品質PDP。 本發明所揭示之內容已在最佳實施形態中詳細說明， · 故同行從業人員可在不脫離本發明之主旨的範圍內可做變 « 更或修改，惟這種變更或修改均屬於本發明之精神所在。 【圖式簡單說明】 第1圖：表示PDP構造之一例的剖面圖。 第2圖：說明PDP用構件之製作例的過程圖，而（a )至（c)係表示形成介電體層的主要過程者。 【主要元件對照表】 1 前面板用玻璃基板 2 背面板用玻璃基板 φ 3 透明電極 4 位址電極 5 透明介電體層 . 6 白色介電體層 7 保護膜 8 隔板 9 螢光體 10 剝離薄膜 34- (29)1296567 11 剝離薄膜 12 裸片 13 片狀形成物Example number Placement time Settling coarse particles presence or absence of particle size measurement machine μ(μπι) Withstand voltage (kV) Applicability Example just after dispersion 4πτ ιΤΠτ j\\\ Almost no 7.5 0.95 〇5 2 weeks later Μ Sichuan, almost no 7.5 After 0.95 〇4 weeks, jfrrr is almost no 7.5 0.95 〇Comparative example just after dispersion >fnT Μ Quite a lot of 25 or more 0.35 X 5 After 2 weeks, there are quite a few 25 or more cannot be measured * X After the comparison example has just been dispersed Μ A lot more than 25 0.39 X 6 After 2 weeks, there are quite a few 25 or more that cannot be measured. * X Comparative example just after dispersion >fmr Μ More than 25 or more 0.44 X 7 After 2 weeks, there are quite a few 25 or more 0.38 X *Failed to form a film. -32- (27) 1296567 It is understood from Table 2 that in Example 5 containing a predetermined amount of the polycarboxylic acid-based polymer compound, a good dispersion state can be maintained for a long period of time. As a result, even when a composition placed for 4 weeks is used to form a dielectric layer, the maximum particle diameter of the glass frit is within an allowable range (20 μm or less), and the formed dielectric layer maintains high withstand voltage characteristics. . On the other hand, in Comparative Example 5 in which no dispersant was present in the composition, it was found that the glass frit caused secondary aggregation, and the withstand voltage was lowered to be self-explanatory. Further, as shown in Comparative Example 6, it is understood that when a polycarboxylic acid-based polymer compound is used as a dispersing agent, if the content is insufficient, it is difficult to maintain a good dispersion state of the composition. Further, as is clear from Comparative Example 7, in the case where the carboxylic acid group present in the molecule is one oleic acid, the dispersion effect is not self-evident. Further, although it was confirmed that the glass frit was settled, the dielectric layer composition after standing for 2 weeks was again stirred again, but each of the compositions failed to return to the state immediately after dispersion. As described above, according to the present invention, the composition for forming a dielectric layer contains a polycarboxylic acid-based polymer compound capable of improving the dispersibility of particles having a high specific gravity such as a glass frit, and the composition can be effectively improved. The dispersion state of the glass frit. Therefore, the composition can be prepared in an excellent dispersion state, and since secondary aggregation of the obtained dispersion liquid can be suppressed, sedimentation does not occur even after storage for a long period of time, and a good dispersion state can be maintained. Further, when the dielectric layer composition of the present invention is diced and adhered to a glass substrate and fired, it is easy to form a dielectric layer having a desired withstand voltage characteristic on the glass substrate. -33- 1296567 (28) When a glass substrate having a dielectric layer having excellent withstand voltage characteristics formed using the dielectric composition of the present invention is used as a member for PDP, it can be used in the case of PDP. The plasma discharge voltage is resistant to high quality PDP with few cell defects. The disclosure of the present invention has been described in detail in the preferred embodiments, and the invention may be modified or modified without departing from the spirit and scope of the invention. The spirit is there. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a PDP structure. Fig. 2 is a process diagram for explaining a production example of a member for PDP, and (a) to (c) show the main processes for forming a dielectric layer. [Main component comparison table] 1 Glass substrate for front panel 2 Glass substrate for back panel φ 3 Transparent electrode 4 Address electrode 5 Transparent dielectric layer. 6 White dielectric layer 7 Protective film 8 Separator 9 Phosphor 10 Peel-off film 34- (29)1296567 11 Release film 12 Die 13 Sheet-like formation
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