201144254 六、發明說明： 【發明所屬之技術領域】 本發明係關於陶瓷胚片用漿料組成物， 合陶瓷電容器。 【先前技術】 在製造層合陶瓷電容器時，一般而言是 。首先，將聚乙烯縮醛樹脂等之黏合劑樹脂 於分散有陶瓷粉末之有機溶劑中，並藉由球 混合而調製出陶瓷胚片用漿料組成物，以流 調製之漿料組成物成形於聚對苯二甲酸乙二 支撐體上，並藉由加熱等來餾除溶劑等後， 離而製造出陶瓷胚片。 此等陶瓷胚片，.是從上述剝離性支撐體 首先，係交互地重疊複數片之藉由網版印刷 的表面形成有成爲內部電極之導電膏而成者 壓著而得層合體。接著藉由各步驟來形成層 爲既定形狀。然後在進行以熱分解來去除該 含之黏合劑成分等之處理，亦即進行所謂的 進行燒結而得陶瓷燒結物，並將外部電極燒 結物的端面上，藉由此步驟，來製造出層合 因此，上述陶瓷胚片，係要求陶瓷胚片用漿 製作業之良好的作業性，以及可承受此等加 強度。 陶瓷胚片及層 進行下列步驟 與可塑劑添加 磨機等均一地 體鑄膜法將所 酯等之剝離性 從支撐體中剝 中剝離使用。 等在陶瓷胚片 ，並進行加熱 合體，並裁切 層合體中所包 脫脂處理後， 結於該陶瓷燒 陶瓷電容器。 料組成物的調 工的各步驟之 -5- 201144254 近年來，隨著電子機器的多功能化和小型化，對於層 合陶瓷電容器亦要求大容量化、小型化。因應於此’陶瓷 胚片中所使用之陶瓷粉末，係採用〇.5μηι以下的細微粒徑 者，並嘗試在剝離性支撐體上可塗佈成5μπι以下的薄膜狀 者。 然而，當使用細微粒徑的陶瓷粉末時，由於充塡密度 和表面積增加，使所使用之黏合劑樹脂量增加，進而使陶 瓷胚片用漿料組成物的黏度亦增大，有時會難以塗佈或產 生陶瓷粉末本身的分散不良。另一方面，在陶瓷胚片製作 時的各步驟中，會受到拉伸和彎曲等之應力負荷，故需採 用具有可承受此般應力之充分強度的黏合劑。 爲了解決此問題，專利文獻1係揭示一種對鹼化度8 0 莫耳％以上之聚乙烯醇的乙烯醇單位，以0.005〜2莫耳％的 比率至少添加二醛來進行縮醛化而成之陶瓷胚片用陶瓷膏 ，而實現一種機械強度佳之陶瓷胚片用漿料組成物。 然而，當以二醛進行交聯時，分子間交聯變得過密， 所得之薄膜胚片的機械強度雖有所提升，但所得之交聯聚 乙烯縮醛樹脂的一部分不溶於有機溶劑，而具有殘存部分 未溶解份之問題。此外，由於交聯部位與未交聯部位的應 力緩和力不同’故具有薄膜胚片產生翹曲之問題。 [先前技術文獻] [專利文獻] 專利文獻1:日本特開2006-282490號公報 201144254 【發明內容】 (發明所欲解決之課題） 本發明係鑒於上述現狀而提供一種可製得具有充分的 機械強度且翹曲少之陶瓷胚片之陶瓷胚片用漿料組成物， 陶瓷胚片及層合陶瓷電容器。 (用以解決課題之手段） 本發明者們係進行精心探討，結果發現到藉由使用聚 合度超過1 000且爲4500以下、乙烯酯單位的含量小於1莫 耳％且縮醛化度爲60〜83莫耳％之聚乙烯縮醛樹脂作爲陶瓷 胚片用漿料組成物的黏合劑樹脂，可形成塗佈性佳之組成 物，即使將厚度薄化，亦可製得機械強度高且不易翹曲之 陶瓷胚片，因而完成本發明。 發明之效果： 能夠提供一種可製得具有充分的機械強度且翹曲少之 陶瓷胚片之陶瓷胚片用漿料組成物，陶瓷胚片及層合陶瓷 電容器》 【實施方式】 以下詳細說明本發明。 本發明中所使用之聚乙烯縮醛樹脂的聚合度，係超過 1000且爲45 00以下。聚合度爲1 000以下時，當製作厚度 2μπι以下的薄膜陶瓷胚片時，機械強度變得不足，聚合度 201144254 超過45 00時，無法充分地溶解於有機溶劑，或是溶液黏度 過高使塗佈性和分散性降低。聚乙烯縮醛樹脂之聚合度的 較佳下限爲1 500，上限爲3500。 上述聚合度，係從聚乙烯縮醛樹脂的製造時所使用之 聚乙烯醇樹脂的黏度平均聚合度，以及聚乙烯縮醛樹脂的 黏度平均聚合度兩者中求取。亦即，由於聚合度不會因縮 醛化而改變，所以聚乙烯醇樹脂與將該聚乙烯醇樹脂進行 縮醛化所得之聚乙烯縮醛樹脂的聚合度相同。雖無特別限 定，但聚乙烯醇樹脂的黏度平均聚合度是指根據ns K6726所求取之平均聚合度。此外，當混合2種以上的聚乙 烯醇樹脂作爲聚乙烯醇樹脂使用時，是指混合後之聚乙烯 醇樹脂全體的表觀黏度平均聚合度。另一方面，聚乙嫌縮 醛樹脂的聚合度，是指根據JIS Κ6728所記載的方法，來 測定將聚乙烯醇樹脂進行縮醛化後之黏度平均聚合度者。 上述聚乙嫌縮醒樹脂之乙嫌醋單位的含量係小於1莫 耳％ ’較佳上限爲0 · 9 9莫耳％。爲1莫耳％以上時，薄膜的 胚片柔軟性過強，而使陶瓷胚片無法保有充分的機械強度 。乙稀酯單位的含量小於1莫耳％之聚乙烯縮醛樹脂，可藉 由將乙稀酯單位的含量小於1莫耳％之聚乙烯醇樹脂，亦即 驗化度高於99莫耳％之聚乙烯醇樹脂進行縮醛化而得。聚 乙烯醇樹脂之鹼化度的較佳下限爲99.01莫耳％。 上述聚乙烯縮醛樹脂之乙烯酯單位的含量之較佳下限 爲0.01莫耳％。乙烯酯單位的含量小於001莫耳％之聚乙烯 縮醒樹脂’可藉由將鹼化度高於99 99莫耳％之聚乙烯醇樹 201144254 脂進行縮醛化而得。鹼化度高於9 9 · 9 9莫耳％之聚乙烯醇， 工業上難以生產出，且對水的溶解性差，有時難以進行縮 醛化反應。因此’聚乙烯醇樹脂之鹼化度的較佳上限爲 9 9.9 9 莫耳 ％。 上述聚乙烯縮醛樹脂之縮醛化度的下限爲60莫耳。/〇， 上限爲83莫耳％。未達60莫耳％時，聚乙烯縮醛樹脂的親 水性高，不易溶解於有機溶劑，對於陶瓷胚片用漿料組成 物的製造形成阻礙，超過8 3莫耳％時，殘存羥基變少，損 及聚乙烯縮醛樹脂的強韌性，就生產性、反應性之觀點來 看，工業上亦難以製得，而導致生產性的降低。縮醛化度 的較佳下限爲65莫耳％，較佳上限爲75莫耳％。 上述聚乙烯縮醛樹脂中所使用之醛類爲單醛（於一分 子內有1個醛基）。當以具有2個以上的醛基之化合物進行 縮醛化時，由於交聯部位與未交聯部位的應力緩和力不同 ’所以在乾燥後從聚對苯二甲酸乙二酯剝離後，有時會產 生翹曲。因此，所使用之醛類較佳爲單醛，即使是使用具 有2個以上的醛基之化合物，相對於聚乙烯醇樹脂的乙烯 醇單位，較佳爲添加少於0.005莫耳％的量，尤佳爲少於 0.003莫耳％的量。 本發明中所使用之聚乙烯縮醛樹脂，通常是以聚乙烯 醇樹脂爲原料來製造出。上述聚乙烯醇樹脂，可藉由以往 所知的手法，亦即使乙烯酯系單體聚合，並將所得之聚合 物進行鹼化而得。使乙烯酯系單體聚合之方法，可使用溶 液聚合法、塊狀聚合法、懸浮聚合法、乳化聚合法等之以 -9 - 201144254 往所知的方法。聚合起始劑，可因應聚合方法來適當地選 擇偶氮系起始劑、過氧化物系起始劑、還原氧化系起始劑 等。鹼化反應，可適用採用有以往所知的鹼觸媒或酸觸媒 之醇解 '水解等，當中，以甲醇爲溶劑並採用氫氧化鈉（ NaOH )之鹼化反應較簡便，故最佳。 乙烯酯系單體，例如可列舉出甲酸乙烯酯、乙酸乙烯 酯、丙酸乙烯酯、丁酸乙烯酯、異丁酸乙烯酯、戊酸乙烯 酯、叔碳酸乙烯酯、己酸乙烯酯、辛酸乙烯酯、月桂酸乙 烯酯、棕櫚酸酸乙烯酯、硬脂酸乙烯酯、油酸乙烯酯、苯 甲酸乙烯酯等，尤佳爲乙酸乙烯酯。 此外，當使前述乙烯酯系單體聚合時，在不損及本發 明的主旨之範圍內，亦可與該他單體共聚合。因此，本發 明之聚乙烯醇樹脂，亦含有由乙烯醇單位與該他單體單位 所構成之槪念。該他單體的例子，例如可列舉出乙烯、丙 烯、正丁烯等之α_烯烴：丙烯酸及該鹽類；丙烯酸甲酯、 丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁 酯、丙烯酸異丁酯、丙烯酸三級丁酯、丙烯酸2-乙基己酯 、丙烯酸十二烷酯、丙烯酸十八烷酯等之丙烯酸酯類；甲 基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲 基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯 、甲基丙烯酸三級丁酯、甲基丙烯酸2-乙基己酯、甲基丙 烯酸十二烷酯、甲基丙烯酸十八烷酯等之甲基丙烯酸酯類 :丙烯醯胺' Ν-甲基丙烯醯胺' Ν-乙基丙烯醯胺、Ν，Ν-二 甲基丙烯醯胺、二丙酮丙烯醯胺、丙烯醯胺丙烷磺酸及該 10· 201144254 鹽類、丙烯醯胺丙基二甲基胺或該酸鹽類或雷 N-羥甲基丙烯醯胺及該衍生物等之丙烯醯胺衍 丙烯醯胺、N -甲基甲基丙烯醯胺、N -乙基甲基 甲基丙烯醯胺丙烷磺酸及該鹽類、甲基丙烯醯 基胺或該酸鹽類或該4級鹽類、N -羥甲基甲基 該衍生物等之甲基丙烯醯胺衍生物；甲基乙烯 烯醚、正丙基乙烯醚、異丙基乙烯醚、正丁基 丁基乙烯醚、三級丁基乙烯醚、十二基乙烯醚 烯醚等之乙烯醚類；丙烯腈、甲基丙烯腈等之 烯、氟乙烯等之鹵化乙烯；偏二氯乙烯、偏二 偏二鹵化乙烯；乙酸烯丙酯、氯化烯丙基等之 物；馬來酸及該鹽類或該酯類或該酐類；乙烯 烷等之乙烯矽烷化合物；乙酸異丙烯酯等。此 對於乙烯酯系單體，通常是以未達10莫耳％的t 縮醛化所使用之酸觸媒並無特別限定，可 或無機酸，例如可列舉出乙酸、對甲苯磺酸、 、鹽酸等。此等當中，較佳爲使用鹽酸、硫酸 佳爲使用鹽酸。 本發明之聚乙烯縮醛樹脂’可藉由下列方 先將3〜1 5質量％濃度的聚乙烯醇樹脂水溶液調 t的溫度範圍，在10~60分鐘間逐漸冷卻該溫 降低至-10〜40 °C時，添加醛及酸觸媒，一邊將 定並在10〜300分鐘間進行縮醛化反應。然後在 間將反應液升溫至45~80°C，並保持該溫度60 〔4級鹽類、 生物：甲基 丙烯醯胺、 胺丙基二甲 丙烯醯胺及 醚、乙基乙 乙烯醚、異 、十八基乙 腈類；氯乙 氟乙烯等之 烯丙基化合 基三甲氧矽 等單體，相 ；：率使用。 使用有機酸 硝酸、硫酸 、硝酸，特 法製得。首 整至80〜100 度》當溫度 溫度保持一 30~200分鐘 ~ 3 6 0分鐘間 -11 - 201144254 。反應的熟化溫度（升溫厚的溫度）較佳爲45°c 4 5 °C更低時，所得之聚乙烯縮醛樹脂的溶液黏度 陶瓷胚片用漿料組成物的分散性降低。接著將該 卻，較佳爲冷卻至室溫，水洗後添加鹼等之中和 行洗淨、乾燥，藉此可得目的之聚乙烯縮醛樹脂 縮醛化度調整爲60〜83莫耳％，必須適當地調整醛 乙烯醇樹脂之添加量，以及添加醛及酸觸媒後的 等。此外，相對於聚乙烯醇100質量份，較佳爲费 質量份的醛。 本發明中，用以將聚乙烯醇樹脂進行縮醛化 無特別限定，例如可列舉出乙醛（包含對乙醛） 丁醛、戊醛、己醛、庚醛、2-乙基己醛、環己醛 醛、苯甲醛、2-甲基苯甲醛、3-甲基苯甲醛、4-醛、對羥基苯甲醛、間羥基苯甲醛、苯基乙醛、 醛等。當中，就生產性與特性均衡之觀點來看， 醛、丁醛。此等醛可單獨使用或倂用2種以上。 所使用之聚乙烯縮醛樹脂，爲使用碳數2〜6的醛 使用碳數2〜4的醛之聚乙烯縮醛樹脂，當中就陶 機械強度、塗佈性之觀點來看，較佳爲使用正丁 烯縮醛樹脂。 本發明之聚乙烯縮醛樹脂中之上述α-烯烴鏈 ’較佳下限爲1莫耳％，較佳上限爲20莫耳％。當 段的含量未達1莫耳％時，含有上述α-烯烴之效果 過2 0莫耳％時’疏水性過強’使陶瓷粉末的分散 以上。較 增高，使 反應液冷 劑，並進 。爲了將 相對於聚 反應時間 I加46〜74 之單醛並 、丙醛、 、咲喃甲 甲基苯甲 β-苯基丙 較佳爲乙 本發明中 ，尤其是 瓷胚片的 醛之聚乙 段的含量 α-烯烴鏈 不足，超 性降低， 201144254 或是由於聚乙烯醇樹脂的溶解性降低，而使縮醛化反應難 以進行。 此外’本發明之陶瓷胚片用漿料組成物，黏合劑樹脂 ’除了上述聚乙烯縮醛樹脂外，亦可含有丙烯酸系樹脂、 纖維素系樹脂。當含有丙烯酸系樹脂、纖維素系樹脂等作 爲黏合劑樹脂時，上述聚乙烯縮醛樹脂於黏合劑樹脂全體 中所佔有之含量的較佳下限爲30質量％。未達30質量％時 ’可能使所得之陶瓷胚片的機械強度變得不足。 本發明中所使用之聚乙烯縮醛樹脂，可藉由將聚合度 超過1〇〇〇且爲4500以下之聚乙烯醇樹脂以醛進行縮醛化而 製造出。當混合使用2種以上的聚乙烯醇樹脂時，各樹脂 之聚合度的平均値爲超過1000且爲4500以下即可。聚合度 的平均値之較佳下限爲1500，上限爲3500» 上述陶瓷粉末並無特別限定，例如可列舉出氧化鋁、 氧化銷、矽酸鋁、氧化鈦、氧化鋅、鈦酸鋇、氧化鎂、賽 隆（SiAlON )、只匕。木厶小歹彳卜、碳化矽、氮化矽、氮 化鋁等粉末。此等陶瓷粉末可單獨使用或併用2種以上。 陶瓷粉末相對於本發明之陶瓷胚片用漿料組成物的全體量 之含量的上限爲80質量％，下限爲30質量％。當陶瓷粉末 的含量少於3 0質量％時，黏度變得過低，使陶瓷胚片成形 時的處理性變差，當多於80質量％時，陶瓷胚片用漿料組 成物的黏度變得過高，捏揉性有降低之傾向。 上述有機溶劑並無特別限定，例如可列舉出丙酮、丁 酮、二丙酮、二異丁酮等之酮類；甲醇、乙醇、異丙醇、 -13- 201144254 丁醇等之醇類；甲苯、二甲苯等之芳香族烴類；丙酸甲酯 、丙酸乙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丁酯 、戊酸甲酯、戊酸乙酯、戊酸丁酯、己酸甲酯、己酸乙酯 、己酸丁酯、乙酸2-乙基己酯、丁酸2-乙基己酯等之酯類 ;甲基溶纖劑、乙基溶纖劑、丁基溶纖劑、α -松油醇'丁 基溶纖劑乙酸酯、丁基卡必醇乙酸酯等。此等有機溶劑可 單獨使用或倂用2種以上。有機溶劑相對於本發明之陶瓷 胚片用漿料組成物的全體量之含量的上限爲80質量％，下 限爲20質量％。位於上述範圍內時，可將適度的捏揉性賦 予至本發明之陶瓷胚片用漿料組成物。當多於80質量％時 ，黏度變得過低，使陶瓷胚片成形時的處理性變差，少於 2 0質量％時，陶瓷胚片用漿料組成物的黏度變得過高，捏 揉性有降低之傾向。 陶瓷胚片用漿料組成物，在不損及本發明的效果之範 圍內，可含有丙烯酸樹脂、纖維素系樹脂等之黏合劑樹脂 、可塑劑、潤滑劑、分散劑、防帶電劑、抗氧化劑等之以 往所知的添加劑。 本發明之陶瓷胚片用漿料組成物，可因應必要添加可 塑劑。所添加之可塑劑的種類並無特別限定，例如可列舉 出鄰苯二甲酸二辛酯、鄰苯二甲酸苯甲基丁酯、鄰苯二甲 酸二丁酯、鄰苯二甲酸二己酯、鄰苯二甲酸二（2-乙基己 基）酯CDOP)、鄰苯二甲酸二（2-乙基丁基）酯等之鄰 苯二甲酸系可塑劑；己二酸二己酯、己二酸二（2_乙基己 基）酯（DO A )等之己二酸系可塑劑；乙二醇、二乙二醇 201144254 、三乙二醇等之二醇系可塑劑；三乙二醇二丁酯、三乙二 醇二（2-乙基丁酯）、三乙二醇二（2-乙基己酯）等之二 醇酯系可塑劑等，此等亦可組合2種以上使用。可塑劑的 使用量並無特別限定，相對於本發明之陶瓷胚片用漿料組 成物的全體量，較佳爲使用〇_1〜10質量％，尤佳爲1~8質量 %。當中就揮發性低且容易保持薄片的柔軟性來看，較佳 爲DOP、DOA、三乙二醇2-乙基己酯。 製造出本發明之使用聚乙烯縮醛樹脂之陶瓷胚片用漿 料組成物的方法並無特別限定，例如可列舉出使用球磨機 、摻合機、三軋輥機等之各種混合機，將含有上述聚乙烯 縮醛樹脂之黏合劑樹脂、陶瓷粉末、有機溶劑、及因應必 要所添加之各種添加劑予以混合之方法。 本發明之陶瓷胚片用漿料組成物，由於具有上述構成 ，即使厚度爲2μ1Ώ以下，亦可製造出具有充分的機械強度 之薄膜陶瓷胚片。如此，使用本發明之陶瓷胚片用漿料組 成物所製得之陶瓷胚片且爲厚度2μιη以下之陶瓷胚片，亦 爲本發明之一。 本發明之陶瓷胚片的製造方法並無特別限定，可藉由 以往所知的製造方法製造，例如可列舉出以流體鑄膜法將 本發明之陶瓷胚片用漿料組成物成形於聚對苯二甲酸乙二 酯等之剝離性支撐體上，並藉由加熱等來餾除溶劑等後， 從支撐體中剝離之方法。 可藉由將塗佈有導電膏之薄層層合於本發明之陶瓷胚 片，而製作出層合陶瓷電容器。如此，使用本發明之陶瓷 -15- 201144254 胚片與導電膏所製得之層合陶瓷電容器，亦爲本發明之一 〇 本發明之層合陶瓷電容器的製造方法並無特別限定， 可藉由以往所知的製造方法製造，例如可列舉出交互地重 疊複數片之藉由網版印刷等在本發明之陶瓷胚片的表面形 成有成爲內部電極之導電裔而成者，並進行加熱壓著而得 層合體，然後在進行以熱分解來去除該層合體中所包含之 黏合劑成分等之處理（脫脂處理）後，進行燒結而得陶瓷 燒結物，並將外部電極燒結於該陶瓷燒結物的端面之方法 等。 此外，上述導電臂的製造方法並無特別限定，可藉由 以往所知的製造方法製造，例如可列舉出將金屬等之導電 性粉末、分散劑、可塑劑、溶劑等混合於聚乙烯縮醛樹脂 之方法等。 以下係列舉出實施例來更詳細地說明本發明，但本發 明並不限定於此等實施例。以下的實施例中，「％」及「 份」在無特別說明時，係意味著「質量％」及「質量份」 〇 聚乙烯縮醛樹脂及抗氧化劑之諸項特性的測定，係依 循下列方法來進行。 (聚乙烯縮醛樹脂的乙烯酯單位含量） 根據JIs K672 8所記載的方法來測定。 (聚乙烯縮醛樹脂的乙烯醇單位含量） 根據JIS K67 28所記載的方法來測定》 -16- 201144254 實施例 (實施例1 ) (聚乙烯縮醛樹脂的調製） 將離子交換水1295g、聚乙烯醇（PVA-1 :聚合度1050 、鹼化度99.2莫耳％ ) 105g裝入於具備回流冷卻器、溫度 計及錨型攪拌翼之內容積2公升的玻璃製容器，將全體升 溫至98 °C使聚乙烯醇完全溶解，而形成聚乙烯醇水溶液（ 濃度7.5質量％ )。將所形成之聚乙烯醇水溶液，一邊以轉 速120rpm持續攪拌並在約30分鐘間逐漸冷卻至5°C後，將 丁醛70g以及作爲丁醛化觸媒的酸觸媒之濃度20質量％的鹽 酸100ml添加於該水溶液中，開始聚乙烯醇的丁醛化。進 行3 0分鐘的丁醛化後，在120分鐘間將全體升溫至70 °C， 並在70 °C下保持180分鐘後，冷卻至室溫。將藉由冷卻所 析出之樹脂過濾後，以離子交換水（相對於樹脂爲1 00倍 量之離子交換水）洗淨複數次，爲了中和而加入0.3質量％ 的氫氧化鈉溶液，在70°C下保持5小時後，進行離心脫水 ’再以100倍量的離子交換水洗淨複數次，脫水後，在40 °C、減壓下進行1 8小時的乾燥，而得聚乙烯丁醛樹脂（ PVB-1 )。所得之聚乙烯丁醛樹脂（pvB-丨），丁醛化度 爲7 1.0莫耳％，乙烯酯單位的含量爲0.8莫耳％，乙烯醇單 位的含量爲2 8.2莫耳％。 將所得之聚乙烯丁醛樹脂10質量份加入於甲苯20質量 份與乙醇20質量份之混合溶劑中，進行攪拌溶解，加入作 -17- 201144254 爲可塑劑之DOP8質量份，進行攪拌溶解。將作爲陶瓷粉 末之鈦酸鋇（堺化學工業公司製，BT-03(平均粒徑〇.3μιη) )1〇〇質量份加入於所得之樹脂溶液，以球磨機混合48小 時’而製得陶瓷胚片用漿料組成物。 (實施例2 ) 除了使用聚乙烯醇（PVA-2 :聚合度1 700、鹼化度 9 9.6莫耳％ )來取代pvA-l之外，其他與實施例！相同而製 得聚乙烯丁醛樹脂（1^8-2)。？乂8-2的丁醛化度爲69.8莫 耳％’乙稀酯單位的含量爲〇.4莫耳％，乙烯醇單位的含量 爲2 9.8莫耳％。接著與實施例1相同地製得陶瓷胚片用漿料 組成物。 (實施例3 ) 除了使用聚乙烯醇（PVA-3 :聚合度24〇〇、鹼化度 "•9莫耳％)來取代PVA-1之外’其他與實施例1相同而製 知聚乙烯丁醛樹脂（pVB_3) 〇ρνΒ_3的丁醛化度爲743莫 耳％乙稀醋單位的含量爲〇. 1莫耳％，乙烯醇單位的含量 爲2 5.6莫耳％ °接著與實施例1相同地製得陶瓷胚片用漿料 組成物。 (實施例4 ) 除了使用聚乙烯醇（pVA_4:聚合度35〇〇、鹼化度 99’8莫耳％ )來取代PVA-1之外，其他與實施例1相同而製 •18- 201144254 得聚乙烯丁醛樹脂（PVB·4)。pvB-4的丁醒化度爲73.2莫 耳％’乙烯酯單位的含量爲〇·2莫耳％，乙烯醇單位的含量 爲2 6.6莫耳％。接著與實施例1相同地製得陶瓷胚片用漿料 組成物。 (實施例5 ) 除了使用聚乙烯醇（PVA-5:聚合度42〇0、鹼化度 99.9莫耳％)來取代pva-〗之外，其他與實施例1相同而製 得聚乙烯丁醛樹脂（PVB-5) 。pvB-5的丁醛化度爲69.0莫 耳％，乙嫌醋單位的含量爲〇.丨莫耳％，乙締醇單位的含量 爲30.9莫耳％。接著，除了添加聚乙烯丁醛樹脂8質量份與 作爲可塑劑之D Ο A 8質量份之外，其他與實施例1相同地製 得陶瓷胚片用漿料組成物。 (實施例6 ) 除了使用聚乙烯醇（PVA-6 :聚合度1*700、鹼化度 99.95莫耳％)來取代pva-1之外，其他與實施例1相同而製 得聚乙烯丁醛樹脂（PVB-6) °pVB-6的丁醛化度爲74_25 莫耳％，乙烯酯單位的含量爲0.05莫耳％，乙烯醇單位的含 量爲25.70莫耳％。接著與實施例1相同地製得陶瓷胚片用 漿料組成物。 (實施例7 ) 除了使用聚乙烯醇（PVA-7 :聚合度1 700、鹼化度 -19- 201144254 99.9莫耳％)來取代PVA-1之外，其他與實施例1相同而製 ί守聚乙嫌丁酸樹脂（ρνΒ·7) .pvb-7的丁醛化度爲80.6莫 耳°/。’乙嫌醋單位的含量爲〇1莫耳％，乙烯醇單位的含量 爲19.3莫耳％。接著與實施例1相同地製得陶瓷胚片用漿料 組成物。 (實施例8 ) 除了使用聚乙烯醇（PVA-8 :聚合度1 700、鹼化度 99_8莫耳％ )來取代ρνΑ·1之外，其他與實施例1相同而製 得聚乙稀丁醛樹脂（1>乂84)。？乂8-8的丁醛化度爲65.2莫 耳％’乙稀酯單位的含量爲0.2莫耳％，乙烯醇單位的含量 爲3 4 · 6莫耳％。接著與實施例1相同地製得陶瓷胚片用漿料 組成物。 (比較例1 ) 除了使用聚乙烯醇（PVA-A :聚合度850、鹼化度99.2 莫耳％ )來取代PVA- 1之外，其他與實施例1相同而製得聚 乙烯丁醛樹脂（PVB-A) 。PVB-A的丁醛化度爲71_0莫耳％ ’乙烯酯單位的含量爲〇.8莫耳％，乙烯醇單位的含量爲 28.2莫耳％。接著與實施例丨相同地製得陶瓷胚片用漿料組 成物。 (比較例2 ) 除了使用聚乙稀醇（PVA-B:聚合度1700、驗化度99 -20- 201144254 莫耳％ )來取代pVA-1之外，其他與實施例1相同而製得聚 乙烯丁醛樹脂（PVB_B) 。PVB-B的丁醛化度爲70莫耳％ ’乙烯酯單位的含量爲1莫耳％，乙烯醇單位的含量爲29莫 耳％ °接著與實施例1相同地製得陶瓷胚片用漿料組成物。 (比較例3 ) 除了使用聚乙烯醇（PVA-C :聚合度3 500、鹼化度 98.5莫耳％)來取代pvA_i之外，其他與實施例1相同而製 得聚乙烯丁醛樹脂（；！^8_(：)。？^-(：的丁醛化度爲71.5 莫耳％’乙烯酯單位的含量爲1.5莫耳％，乙烯醇單位的含 量爲2?莫耳％。接著與實施例1相同地製得陶瓷胚片用漿料 組成物。 (比較例4 ) 除了使用聚乙烯醇（PVA-D :聚合度4800、鹼化度 99.9莫耳％ )來取代PVA-1之外，其他與實施例1相同而製 得聚乙烯丁醛樹脂（！^8-0)。？乂8-0的丁醛化度爲71.9 莫耳％’乙烯酯單位的含量爲0.1莫耳％，乙烯醇單位的含 量爲28莫耳％。接著與實施例1相同地製得陶瓷胚片用漿料 組成物’但漿液的黏度高，塗佈性差，而在胚片中觀察到 粒子分散性的不均一。 (比較例5 ) 除了使用聚乙烯醇（PVA-E :聚合度2400、鹼化度 -21 - 201144254 99.9莫耳％)來取代pvA-i，並與丁醛同時添加戊二醛 0.08 g之外’其他與實施例1相同而製得聚乙烯丁醛樹脂（ PVB-E) 。PVB-E的丁醛化度爲71.9莫耳％，乙烯酯單位的 含量爲0.1莫耳％ ’乙烯醇單位的含量爲28莫耳％。接著與 實施例1相同地製得陶瓷胚片用漿料組成物。 (比較例6 ) 除了使用聚乙烯醇（PVA-F :聚合度1 700、鹼化度 9 9.5莫耳％ )來取代p v A -1之外，其他與比較例5相同而製 得聚乙烯丁醛樹脂（PVB-F) "PVB-F的丁醛化度爲71.0莫 耳％’乙烯酯單位的含量爲〇_5莫耳％，乙烯醇單位的含量 爲2 8 _ 5莫耳％。接著與實施例1相同地製得陶瓷胚片用漿料 組成物。 使用塗佈棒，將實施例1〜8及比較例1〜6中所製作之陶 瓷胚片用漿料組成物，以使乾燥厚度成爲2μηι之方式塗佈 在經脫模處理後的聚酯薄膜上，在常溫下進行1小時的風 乾後，以熱風乾燥機在80 °C下進行3小時，接著在120。(：下 進行2小時的乾燥而製得陶瓷胚片。 (評估） (機械強度的評估） 從聚酯薄膜中將所得之陶瓷胚片剝離，觀察陶瓷胚片 的狀態。並以下列2階段進行評估。 〇：陶瓷胚片上未觀察到斷裂或破損 -22- 201144254 X :雖僅有些微但已觀察到斷裂或破損 (胚片評估） 從聚對苯二甲酸乙二酯中，將陶瓷胚片裁切爲6 0mm X 5 0 m m的大小，在2 0 °C下放置3分鐘後，以光學顯微鏡觀測 薄片的側面。並以下列2階段進行評估。 〇：未觀察到陶瓷胚片的翹曲 X:雖僅有些微但已在陶瓷胚片上觀察到翹曲 機械強度的評估與胚片評估之結果如第1表所示。 -23- 201144254 [第1表] 願 O O 0 0 ο 0 〇 〇 0 〇 ο 0 X X 擗 m 锻 m o 〇 0 ο ο ο 〇 0 X X X X 0 ο 趙呂 1 i膜 摧 摧 堞 鹿 壊 摧 鹿 壊 m 壊 壊 m 擗 诹 m s 8 s s 8 s S S s s S 含 g δ •«e ο ΚΙ ?： s J5 ro s S LA <0 P： o P： f= Ρ： m m 躍 s o § o ο ο s o ο ο g o 〇 〇 S 〇 s d 8 s ο ο ο ο S ο 跋 K) a赵？ gSi s s s s 芑 o S o o ο ο δ 蔽 s s s s R a 〇> a 〇> CM S3 οό CM οό eg η <π s o o ο o t£? Ο § o s 〇 〇 s o o s Ο 9 1 ο m cvi CO m 1ι -L CM ± CO ± I ΙΑ -1 Ϊ 00 Λ ί Ϊ 2 1 UJ % I l I Έ I έ g 安 〇. I 1 g 1 t 1 m i CSl C9 m 握 寸 10 (0 卜 S 00 i N CD 寸 U) to 闺 握 辑 辑 闺 闺 辑 鎰 鎰 鎰 鑑 鎰 鎰 M 佩 1¾ Μ 卹 IK Μ Μ Μ a 產業上之可利用性： 根據本發明，能夠提供一種可製得具有充分的機械強 -24- 201144254 度且翹曲少之陶瓷胚片之陶瓷胚片用漿料組成物，陶瓷胚 片及層合陶瓷電容器。201144254 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a slurry composition for ceramic green sheets, and a ceramic capacitor. [Prior Art] When manufacturing a laminated ceramic capacitor, it is generally. First, a binder resin such as a polyvinyl acetal resin is placed in an organic solvent in which a ceramic powder is dispersed, and a slurry composition for a ceramic green sheet is prepared by ball mixing, and a slurry composition prepared by a flow is formed. On the polyethylene terephthalate support, a solvent or the like is distilled off by heating or the like, and then a ceramic green sheet is produced. These ceramic green sheets are obtained by first adhering a plurality of sheets of a conductive paste which is an internal electrode by forming a conductive paste which is an internal electrode by alternately laminating a plurality of sheets. The layers are then formed into a predetermined shape by each step. Then, a treatment for removing the binder component or the like by thermal decomposition is performed, that is, a so-called sintering is performed to obtain a ceramic sintered body, and the end face of the external electrode sintered body is subjected to the steps to produce a layer. Therefore, the ceramic green sheets described above are required to have good workability in the slurry working of the ceramic green sheets, and can withstand such reinforcing strength. Ceramic green sheets and layers The following steps were carried out to remove the peeling property of the ester or the like from the support by a uniform casting method such as a plasticizer-adding mill. Waiting in the ceramic green sheet, and heating the composite, and cutting the degreased coating in the laminate, the ceramic ceramic capacitor is sealed. -5-201144254 In recent years, with the versatility and miniaturization of electronic equipment, large-capacity and miniaturization are required for laminated ceramic capacitors. In the case of the ceramic powder used in the ceramic green sheet, a fine particle size of 〇.5 μη or less is used, and it is attempted to apply a film having a thickness of 5 μm or less to the peelable support. However, when a ceramic powder having a fine particle diameter is used, the amount of the binder resin to be used is increased due to an increase in the density and surface area, and the viscosity of the slurry composition for ceramic green sheets is also increased, which may be difficult. The coating or the ceramic powder itself is poorly dispersed. On the other hand, in each step of the production of the ceramic green sheet, a stress load such as stretching and bending is required, and therefore an adhesive having a sufficient strength to withstand such stress is required. In order to solve this problem, Patent Document 1 discloses a vinyl alcohol unit of polyvinyl alcohol having a degree of alkalinity of 80% or more, which is obtained by acetalizing at least a dialdehyde at a ratio of 0.005 to 2 mol%. The ceramic green sheet is made of a ceramic paste, and a slurry composition for ceramic green sheets having good mechanical strength is realized. However, when crosslinking is carried out with dialdehyde, the intermolecular crosslinking becomes too dense, and although the mechanical strength of the obtained film green sheet is improved, a part of the obtained crosslinked polyethylene acetal resin is insoluble in an organic solvent, and There is a problem that the remaining portion is not dissolved. Further, since the stress relaxation force of the crosslinked portion and the uncrosslinked portion is different, there is a problem that the film green sheet is warped. [Prior Art] [Patent Document 1] JP-A-2006-282490 (Technical Problem) The present invention provides a machine that can be manufactured in view of the above-described state of the art. A slurry composition for ceramic green sheets of ceramic green sheets having low strength and warpage, ceramic green sheets and laminated ceramic capacitors. (Means for Solving the Problems) The inventors of the present invention conducted intensive studies and found that the degree of polymerization exceeds 1,000 and is less than 4500, the content of vinyl ester units is less than 1 mol%, and the degree of acetalization is 60. ～83 mol% of a polyvinyl acetal resin as a binder resin for a slurry composition for a ceramic green sheet, can form a composition having good coatability, and even if the thickness is thinned, mechanical strength and high warpage can be obtained. The ceramic lamella of Qufu, thus completing the present invention. Advantageous Effects of Invention: It is possible to provide a slurry composition for a ceramic green sheet which can have a ceramic green sheet having sufficient mechanical strength and a small warpage, a ceramic green sheet and a laminated ceramic capacitor. [Embodiment] Hereinafter, the present invention will be described in detail. invention. The degree of polymerization of the polyvinyl acetal resin used in the present invention is more than 1,000 and not more than 50,000. When the degree of polymerization is 1 000 or less, when a thin film ceramic green sheet having a thickness of 2 μm or less is produced, the mechanical strength is insufficient, and when the degree of polymerization 201144254 exceeds 50,000, the organic solvent is not sufficiently dissolved, or the solution viscosity is too high to be coated. Cloth and dispersion are reduced. The preferred lower limit of the degree of polymerization of the polyvinyl acetal resin is 1,500, and the upper limit is 3,500. The degree of polymerization is determined from both the viscosity average degree of polymerization of the polyvinyl alcohol resin used in the production of the polyvinyl acetal resin and the viscosity average degree of polymerization of the polyvinyl acetal resin. That is, since the degree of polymerization is not changed by acetalization, the degree of polymerization of the polyvinyl acetal resin obtained by acetalizing the polyvinyl alcohol resin is the same. Although not particularly limited, the viscosity average degree of polymerization of the polyvinyl alcohol resin means the average degree of polymerization determined according to ns K6726. Further, when two or more types of polyvinyl alcohol resins are used as the polyvinyl alcohol resin, the average viscosity degree of the apparent viscosity of the entire polyvinyl alcohol resin after mixing is referred to. On the other hand, the degree of polymerization of the polyacetal acetal resin is determined by measuring the viscosity average degree of polymerization after acetalization of the polyvinyl alcohol resin according to the method described in JIS Κ6728. The content of the B vinegar unit of the above-mentioned polyethylenic acid repellent resin is less than 1 mol% ‘the upper limit is preferably 0.99 mol%. When it is 1 mol% or more, the green sheet of the film is too soft, and the ceramic green sheet cannot maintain sufficient mechanical strength. A polyvinyl acetal resin having a content of ethylene ester unit of less than 1 mol%, which may be a polyvinyl alcohol resin having a content of ethylene ester unit of less than 1 mol%, that is, a degree of verification higher than 99 mol% The polyvinyl alcohol resin is obtained by acetalization. A preferred lower limit of the degree of alkalization of the polyvinyl alcohol resin is 99.01 mol%. A preferred lower limit of the content of the vinyl ester unit of the polyvinyl acetal resin is 0.01 mol%. A polyethylene reticular resin having a vinyl ester unit content of less than 001 mol% can be obtained by acetalization of a polyvinyl alcohol tree 201144254 fat having a degree of alkalinity higher than 99 99 mol%. Polyvinyl alcohol having a degree of alkalinity of more than 99.9% is industrially difficult to produce, and solubility in water is poor, and it is sometimes difficult to carry out a acetalization reaction. Therefore, the preferred upper limit of the degree of alkalization of the polyvinyl alcohol resin is 9 9.9 9 mol%. The lower limit of the degree of acetalization of the above polyvinyl acetal resin is 60 moles. /〇, the upper limit is 83%. When the amount is less than 60% by mole, the polyvinyl acetal resin has high hydrophilicity and is not easily dissolved in an organic solvent, which hinders the production of a slurry composition for a ceramic green sheet. When it exceeds 83% by mole, the residual hydroxyl group decreases. The strength and toughness of the polyvinyl acetal resin are impaired, and industrially, it is difficult to produce from the viewpoint of productivity and reactivity, resulting in a decrease in productivity. A preferred lower limit of the degree of acetalization is 65 mol%, and a preferred upper limit is 75 mol%. The aldehyde used in the above polyvinyl acetal resin is a monoaldehyde (one aldehyde group in one molecule). When acetalization is carried out with a compound having two or more aldehyde groups, the stress relaxation force of the crosslinked portion and the uncrosslinked portion is different. Therefore, after being peeled off from polyethylene terephthalate after drying, sometimes Warp will occur. Therefore, the aldehyde to be used is preferably a monoaldehyde, and even if a compound having two or more aldehyde groups is used, it is preferably added in an amount of less than 0.005 mol% based on the vinyl alcohol unit of the polyvinyl alcohol resin. More preferably, it is less than 0.003 mol%. The polyvinyl acetal resin used in the present invention is usually produced by using a polyvinyl alcohol resin as a raw material. The polyvinyl alcohol resin can be obtained by subjecting the obtained polymer to alkalization by a conventionally known method, even if a vinyl ester monomer is polymerized. The method of polymerizing the vinyl ester monomer can be carried out by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method in the manner of -9 - 201144254. The polymerization initiator can be appropriately selected from the group consisting of an azo initiator, a peroxide initiator, a reducing oxidation initiator, and the like in accordance with the polymerization method. The alkalization reaction can be applied to the alcoholysis hydrolysis of a conventionally known base catalyst or acid catalyst. Among them, the alkalization reaction using methanol as a solvent and sodium hydroxide (NaOH) is relatively simple, so it is optimal. . Examples of the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl versatate, vinyl hexanoate, and octanoic acid. Vinyl ester, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate, etc., particularly preferably vinyl acetate. Further, when the vinyl ester monomer is polymerized, it may be copolymerized with the other monomer within the range not impairing the gist of the present invention. Therefore, the polyvinyl alcohol resin of the present invention also contains a concept consisting of a vinyl alcohol unit and the other monomer unit. Examples of the other monomer include, for example, α-olefins such as ethylene, propylene, and n-butene: acrylic acid and the salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and acrylic acid. Acrylates such as butyl ester, isobutyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.; methyl methacrylate, ethyl methacrylate , n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Methacrylates such as dodecyl ester, octadecyl methacrylate, etc.: acrylamide Ν-methacrylamide Ν-ethyl acrylamide, hydrazine, hydrazine-dimethyl methacrylate Diacetone acrylamide, acrylamide propylene sulfonic acid, and the above-mentioned 10·201144254 salt, acrylamidopropyldimethylamine or the acid salt or the N-methylol decylamine and the derivative thereof Acrylamide, propyleneamine, N-methylmethacrylamide, N-B Methyl methacrylamide amide sulfonic acid and the salt thereof, methacryl decylamine or the methacrylamide such as the acid salt or the quaternary salt, the N-methylolmethyl derivative or the like Derivatives; vinyl ethers such as methyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl butyl vinyl ether, tert-butyl butyl vinyl ether, dodecyl vinyl ether ether, etc.; a halogenated ethylene such as a nitrile or a methacrylonitrile; a vinyl halide such as a vinyl fluoride; a vinylidene chloride or a vinylidene dihalide; an allyl acetate; an allyl chloride; the maleic acid and the salt Or the ester or the anhydride; a vinyl decane compound such as vinyl hydride; isopropenyl acetate or the like. The vinyl ester monomer is usually not particularly limited as long as the acid catalyst used for the acetalization of less than 10 mol%, and the inorganic acid may be, for example, acetic acid or p-toluenesulfonic acid. Hydrochloric acid, etc. Among these, it is preferred to use hydrochloric acid or sulfuric acid to preferably use hydrochloric acid. The polyvinyl acetal resin of the present invention can be cooled by the following method to adjust the temperature range of the aqueous solution of the polyvinyl alcohol resin of 3 to 15% by mass, and gradually reduce the temperature to -10~ during 10 to 60 minutes. At 40 ° C, an aldehyde and an acid catalyst were added, and the acetalization reaction was carried out for 10 to 300 minutes. Then, the reaction solution is heated to 45-80 ° C, and the temperature is maintained at 60 [4 grades of salts, organisms: methacrylamide, amine propyl methacrylamide and ether, ethyl vinyl ether, Monovalent, octadecyl acetonitrile; allylic vinyltricarboxylate such as chloroethylene fluoride, etc., phase; It is prepared by using an organic acid such as nitric acid, sulfuric acid or nitric acid. The first time to 80~100 degrees" when the temperature is maintained for 30~200 minutes ~ 3 6 0 minutes -11 - 201144254. When the aging temperature (temperature at which the temperature is raised) of the reaction is preferably 45 ° C 4 5 ° C, the solution viscosity of the obtained polyvinyl acetal resin is lowered, and the dispersibility of the slurry composition for ceramic green sheets is lowered. Next, it is preferably cooled to room temperature, washed with water, added with a base or the like, washed and dried, whereby the degree of acetalization of the desired polyvinyl acetal resin is adjusted to 60 to 83 mol%. The amount of the aldehyde vinyl alcohol resin to be added, and the addition of the aldehyde and the acid catalyst must be appropriately adjusted. Further, it is preferably a part by mass of the aldehyde with respect to 100 parts by mass of the polyvinyl alcohol. In the present invention, the acetalization of the polyvinyl alcohol resin is not particularly limited, and examples thereof include acetaldehyde (including p-acetaldehyde) butyraldehyde, valeraldehyde, hexanal, heptaldehyde, and 2-ethylhexanal. Cyclohexanal, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-aldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, aldehyde, and the like. Among them, in terms of balance between productivity and characteristics, aldehydes and butyraldehyde. These aldehydes may be used alone or in combination of two or more. The polyvinyl acetal resin to be used is a polyvinyl acetal resin having an aldehyde having 2 to 4 carbon atoms and having an aldehyde having 2 to 6 carbon atoms. From the viewpoint of mechanical strength and coatability, it is preferably A n-butene acetal resin is used. The lower limit of the above α-olefin chain in the polyvinyl acetal resin of the present invention is preferably 1 mol%, and the upper limit is preferably 20 mol%. When the content of the segment is less than 1 mol%, when the effect of the above α-olefin is more than 20 mol%, the "hydrophobicity is too strong" to disperse the ceramic powder or more. The increase is made, so that the reaction liquid is cooled. In order to add 46-74 to the polymerization reaction time I, the monoaldehyde, propionaldehyde, and m-methylmethylbenzyl beta-phenylpropene are preferably in the present invention, especially the aldehyde aggregation of the porcelain slab. The content of the segment B is insufficient in the α-olefin chain, and the super-reduction is lowered. 201144254 Or the solubility of the polyvinyl alcohol resin is lowered, and the acetalization reaction is difficult to proceed. Further, the "slurry composition for ceramic green sheets of the present invention, the binder resin" may contain an acrylic resin or a cellulose resin in addition to the polyethylene acetal resin. When an acrylic resin, a cellulose resin or the like is used as the binder resin, a preferred lower limit of the content of the polyvinyl acetal resin in the entire binder resin is 30% by mass. When the amount is less than 30% by mass, the mechanical strength of the obtained ceramic green sheets may be insufficient. The polyvinyl acetal resin used in the present invention can be produced by acetalizing a polyvinyl alcohol resin having a polymerization degree of more than 1 Torr and 4,500 or less in an aldehyde. When two or more kinds of polyvinyl alcohol resins are used in combination, the average degree of polymerization of each resin may be more than 1,000 and not more than 4500. The preferred lower limit of the average degree of polymerization is 1,500, and the upper limit is 3500. The above ceramic powder is not particularly limited, and examples thereof include alumina, oxidation pin, aluminum niobate, titanium oxide, zinc oxide, barium titanate, and magnesium oxide. , Silong (SiAlON), only 匕. Powder such as hibiscus, tantalum carbide, tantalum nitride, aluminum nitride, etc. These ceramic powders may be used alone or in combination of two or more. The upper limit of the content of the ceramic powder with respect to the total amount of the slurry composition for ceramic green sheets of the present invention is 80% by mass, and the lower limit is 30% by mass. When the content of the ceramic powder is less than 30% by mass, the viscosity becomes too low, and the handleability at the time of forming the ceramic green sheet is deteriorated. When it is more than 80% by mass, the viscosity of the slurry composition for ceramic green sheets becomes Too high, the tendency to pinch is reduced. The organic solvent is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, diacetone, and diisobutyl ketone; alcohols such as methanol, ethanol, isopropyl alcohol, and -13-201144254 butanol; toluene; Aromatic hydrocarbons such as xylene; methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, methyl valerate, ethyl valerate, pentane Ester of butyl acrylate, methyl hexanoate, ethyl hexanoate, butyl hexanoate, 2-ethylhexyl acetate, 2-ethylhexyl butyrate; methyl cellosolve, ethyl cellosolve Agent, butyl cellosolve, α-terpineol 'butyl cellosolve acetate, butyl carbitol acetate, and the like. These organic solvents may be used singly or in combination of two or more. The upper limit of the content of the organic solvent relative to the total amount of the slurry composition for ceramic green sheets of the present invention is 80% by mass, and the lower limit is 20% by mass. When it is in the above range, moderate kneading property can be imparted to the slurry composition for ceramic green sheets of the present invention. When the amount is more than 80% by mass, the viscosity becomes too low, and the handleability at the time of molding the ceramic green sheet is deteriorated. When the amount is less than 20% by mass, the viscosity of the slurry composition for ceramic green sheets becomes too high, and the pinch is too high. There is a tendency to reduce temperament. The slurry composition for ceramic green sheets may contain a binder resin such as an acrylic resin or a cellulose resin, a plasticizer, a lubricant, a dispersant, an antistatic agent, and an anti-corrosion agent within a range that does not impair the effects of the present invention. A conventionally known additive such as an oxidizing agent. The slurry composition for ceramic green sheets of the present invention may be added with a plasticizer as necessary. The type of the plasticizer to be added is not particularly limited, and examples thereof include dioctyl phthalate, benzyl butyl phthalate, dibutyl phthalate, and dihexyl phthalate. a phthalic acid plasticizer such as di(2-ethylhexyl) phthalate (CDOP) or bis(2-ethylbutyl) phthalate; dihexyl adipate and adipic acid Adipic acid plasticizer such as di(2-ethylhexyl) ester (DO A ); glycol-based plasticizer such as ethylene glycol, diethylene glycol 201144254, triethylene glycol, etc.; A glycol ester-based plasticizer such as an ester, a triethylene glycol bis(2-ethylbutyl acrylate) or a triethylene glycol bis(2-ethylhexyl ester) may be used in combination of two or more kinds. The amount of the plasticizer to be used is not particularly limited, and is preferably 〇1 to 10% by mass, particularly preferably 1 to 8% by mass, based on the total amount of the slurry composition for ceramic green sheets of the present invention. Among them, DOP, DOA, and triethylene glycol 2-ethylhexyl ester are preferred in view of low volatility and easy maintenance of the softness of the sheet. The method for producing a slurry composition for a ceramic green sheet using a polyvinyl acetal resin of the present invention is not particularly limited, and examples thereof include various mixers using a ball mill, a blender, and a three-roller. A method of mixing a binder resin of a polyvinyl acetal resin, a ceramic powder, an organic solvent, and various additives added as necessary. According to the slurry composition for ceramic green sheets of the present invention, even if the thickness is 2 μm or less, a thin film ceramic green sheet having sufficient mechanical strength can be produced. Thus, the ceramic green sheet obtained by using the slurry composition for ceramic green sheets of the present invention and having a ceramic green sheet having a thickness of 2 μm or less is also one of the inventions. The method for producing the ceramic green sheet of the present invention is not particularly limited, and it can be produced by a conventionally known production method. For example, the slurry composition for ceramic green sheets of the present invention can be formed into a pair by a fluid casting method. A method in which a solvent or the like is distilled off by a heating or the like on a peelable support such as ethylene phthalate, and then peeled off from the support. A laminated ceramic capacitor can be produced by laminating a thin layer coated with a conductive paste on the ceramic green sheet of the present invention. Thus, the laminated ceramic capacitor obtained by using the ceramic -15-201144254 embryo chip and the conductive paste of the present invention is also one of the inventions. The method for manufacturing the laminated ceramic capacitor of the present invention is not particularly limited, and In the production method of the conventionally known method, for example, a conductive material in which an internal electrode is formed on the surface of the ceramic green sheet of the present invention by screen printing or the like by alternately stacking a plurality of sheets is used, and heating and pressing are performed. Then, a laminate is obtained, and then a treatment (degreasing treatment) for removing the binder component or the like contained in the laminate by thermal decomposition is performed, followed by sintering to obtain a ceramic sintered body, and the external electrode is sintered to the ceramic sintered body. The method of the end face, etc. In addition, the method for producing the conductive arm is not particularly limited, and it can be produced by a conventionally known production method, and for example, a conductive powder such as a metal, a dispersant, a plasticizer, a solvent, or the like is mixed with the polyvinyl acetal. Resin method, etc. The invention is described in more detail in the following examples, but the invention is not limited thereto. In the following examples, "%" and "parts" mean "% by mass" and "parts by mass". The measurement of the properties of polyvinyl acetal resin and antioxidants is based on the following. The method is carried out. (Vinyl ester unit content of polyvinyl acetal resin) Measured according to the method described in JIS K672 8. (Vinyl Alcohol Unit Content of Polyvinyl Acetal Resin) Measured according to the method described in JIS K67 28 Example - 16- 201144254 Example (Example 1) (Preparation of Polyvinyl Acetal Resin) 1295 g of ion-exchanged water was collected. Vinyl alcohol (PVA-1: degree of polymerization: 1050, degree of alkalinity: 99.2 mol%) 105 g was placed in a glass container having an internal volume of 2 liters equipped with a reflux condenser, a thermometer, and an anchor type stirring blade, and the whole temperature was raised to 98 °. C completely dissolves the polyvinyl alcohol to form an aqueous polyvinyl alcohol solution (concentration: 7.5% by mass). The formed polyvinyl alcohol aqueous solution was continuously stirred at a number of revolutions of 120 rpm and gradually cooled to 5 ° C in about 30 minutes, and then the concentration of 70 g of butyraldehyde and the acid catalyst as a butyralization catalyst was 20% by mass. 100 ml of hydrochloric acid was added to the aqueous solution to initiate butyraldehyde formation of polyvinyl alcohol. After 30 minutes of butyraldehydeization, the whole was heated to 70 ° C for 120 minutes, and held at 70 ° C for 180 minutes, and then cooled to room temperature. After filtering the resin precipitated by cooling, it was washed several times with ion-exchanged water (ion exchange water in an amount of 100 times with respect to the resin), and a 0.3 mass% sodium hydroxide solution was added for neutralization, at 70 After 5 hours at ° C, centrifugal dehydration was carried out, and then washed with 100 times of ion-exchanged water for several times. After dehydration, it was dried at 40 ° C under reduced pressure for 18 hours to obtain polyvinyl butyral. Resin (PVB-1). The obtained polyvinyl butyral resin (pvB-丨) had a degree of butyralization of 7 1.0 mol%, a vinyl ester unit content of 0.8 mol%, and a vinyl alcohol unit content of 28.2 mol%. 10 parts by mass of the obtained polyvinyl butyral resin was added to a mixed solvent of 20 parts by mass of toluene and 20 parts by mass of ethanol, and the mixture was stirred and dissolved, and 8 parts by mass of DOP as a plasticizer was added as -17 to 201144254, and stirred and dissolved. A ceramic powder, barium titanate (BT-03 (average particle size 〇.3μιη), manufactured by Nippon Chemical Industry Co., Ltd.) was added to the obtained resin solution, and mixed in a ball mill for 48 hours to obtain a ceramic embryo. A slurry composition for tablets. (Example 2) In addition to the use of polyvinyl alcohol (PVA-2: degree of polymerization 1 700, degree of alkalinity 9 9.6 mol%) in place of pvA-1, other examples and examples! The same was made of a polyvinyl butyral resin (1^8-2). ? The butyraldehyde degree of 乂8-2 was 69.8 mol%, the content of the ethyl ester unit was 〇.4 mol%, and the content of the vinyl alcohol unit was 29.8 mol%. Then, a slurry composition for ceramic green sheets was obtained in the same manner as in Example 1. (Example 3) The same procedure as in Example 1 except that polyvinyl alcohol (PVA-3: degree of polymerization: 24 Å, degree of alkalinity " 9 mole %) was used instead of PVA-1 The butyraldehyde degree of the ethylene butyral resin (pVB_3) 〇ρνΒ_3 was 743 mol%, and the content of the ethylene vinegar unit was 〇. 1 mol%, and the content of the vinyl alcohol unit was 2 5.6 mol%. Then, with Example 1 A slurry composition for ceramic green sheets was obtained in the same manner. (Example 4) The same procedure as in Example 1 was carried out except that polyvinyl alcohol (pVA_4: degree of polymerization 35 〇〇, degree of alkalinity 99'8 mol%) was used instead of PVA-1. 18-201144254 Polyvinyl butyral resin (PVB·4). The degree of waking degree of pvB-4 was 73.2 mol%, the content of vinyl ester unit was 〇·2 mol%, and the content of vinyl alcohol unit was 2 6.6 mol%. Then, a slurry composition for ceramic green sheets was obtained in the same manner as in Example 1. (Example 5) A polyvinyl butyral was produced in the same manner as in Example 1 except that polyvinyl alcohol (PVA-5: degree of polymerization: 42 〇 0, degree of alkalinity: 99.9 mol%) was used instead of pva-. Resin (PVB-5). The degree of butyralization of pvB-5 was 69.0 mol%, and the content of the vinegar unit was 〇.丨mol%, and the content of the propylene glycol unit was 30.9 mol%. Then, a slurry composition for ceramic green sheets was prepared in the same manner as in Example 1 except that 8 parts by mass of a polyvinyl butyral resin and 8 parts by mass of D Ο A as a plasticizer were added. (Example 6) A polyvinyl butyral was produced in the same manner as in Example 1 except that polyvinyl alcohol (PVA-6: degree of polymerization 1*700, degree of alkalinity: 99.95 mol%) was used instead of pva-1. The resin (PVB-6) °pVB-6 had a degree of butyralization of 74 to 25 mol%, a vinyl ester unit content of 0.05 mol%, and a vinyl alcohol unit content of 25.70 mol%. Then, a slurry composition for ceramic green sheets was obtained in the same manner as in Example 1. (Example 7) The same procedure as in Example 1 was carried out except that polyvinyl alcohol (PVA-7: degree of polymerization 1 700, degree of alkalinity -19 - 201144254 99.9 mol%) was used instead of PVA-1. Polyethylene succinic acid (ρνΒ·7) . pvb-7 has a degree of butyralization of 80.6 mol/. The content of the B vinegar unit is 〇1 mol%, and the content of the vinyl alcohol unit is 19.3 mol%. Then, a slurry composition for ceramic green sheets was obtained in the same manner as in Example 1. (Example 8) Polyethylene butyraldehyde was produced in the same manner as in Example 1 except that polyvinyl alcohol (PVA-8: degree of polymerization: 1700, degree of alkalinity: 99_8 mol%) was used instead of ρνΑ·1. Resin (1 > 乂 84). ? The butyraldehyde degree of 乂8-8 was 65.2 mol%, the content of the ethyl ester unit was 0.2 mol%, and the content of the vinyl alcohol unit was 34. 6 mol%. Then, a slurry composition for ceramic green sheets was obtained in the same manner as in Example 1. (Comparative Example 1) A polyvinyl butyral resin was obtained in the same manner as in Example 1 except that polyvinyl alcohol (PVA-A: degree of polymerization 850, degree of alkalinity: 99.2% by mole) was used instead of PVA-1. PVB-A). The degree of butyralization of PVB-A was 71 _0 mol%. The content of the vinyl ester unit was 〇.8 mol%, and the content of the vinyl alcohol unit was 28.2 mol%. Then, a slurry composition for ceramic green sheets was obtained in the same manner as in Example 。. (Comparative Example 2) The same procedure as in Example 1 was carried out except that polyethylene glycol (PVA-B: degree of polymerization 1700, degree of polymerization 99 -20 to 201144254 mol%) was used instead of pVA-1. Vinyl butyral resin (PVB_B). The degree of butyralization of PVB-B was 70 mol%, the content of the vinyl ester unit was 1 mol%, and the content of the vinyl alcohol unit was 29 mol%. Then, the slurry for ceramic green sheets was obtained in the same manner as in Example 1. Material composition. (Comparative Example 3) A polyvinyl butyral resin was obtained in the same manner as in Example 1 except that polyvinyl alcohol (PVA-C: degree of polymerization: 3,500, degree of alkalinity: 98.5 mol%) was used instead of pvA_i (; !^8_(:). ^^-(: The degree of butyralization is 71.5% by mole of the vinyl ester unit content is 1.5 mol%, and the content of the vinyl alcohol unit is 2 mol%. Next, with the examples 1 A slurry composition for ceramic green sheets was obtained in the same manner. (Comparative Example 4) Except that polyvinyl alcohol (PVA-D: degree of polymerization 4800, degree of alkalinity: 99.9 mol%) was used instead of PVA-1, A polyvinyl butyral resin (!^8-0) was obtained in the same manner as in Example 1. The butyraldehyde degree of ?8-0 was 71.9 mol%, the content of the vinyl ester unit was 0.1 mol%, and vinyl alcohol The content of the unit was 28 mol%. Then, the slurry composition for ceramic green sheets was obtained in the same manner as in Example 1 except that the viscosity of the slurry was high, and the coatability was poor, and unevenness in particle dispersibility was observed in the green sheets. (Comparative Example 5) In place of pvA-i, polyvinyl alcohol (PVA-E: degree of polymerization 2400, degree of alkalinity - 21,044,454, 99.9 mol%) was used, and it was added simultaneously with butyraldehyde. A polyvinyl butyral resin (PVB-E) was prepared in the same manner as in Example 1 except that glutaraldehyde was added in an amount of 0.08 g. The degree of butyralization of PVB-E was 71.9 mol%, and the content of vinyl ester unit was 0.1. The content of the molar % 'vinyl alcohol unit was 28 mol%. Then, a slurry composition for ceramic green sheets was obtained in the same manner as in Example 1. (Comparative Example 6) Except that polyvinyl alcohol (PVA-F: degree of polymerization) was used. The degree of butyralization of polyvinyl butyral resin (PVB-F) "PVB-F was obtained in the same manner as in Comparative Example 5 except that 1 700, the degree of alkalinity was 9 9.5 mol%) instead of pv A -1 . The content of the 71.0 mol % 'vinyl ester unit was 〇 5 mol %, and the content of the vinyl alcohol unit was 2 8 _ 5 mol %. Then, the slurry composition for ceramic green sheets was obtained in the same manner as in Example 1. The slurry composition for ceramic green sheets prepared in Examples 1 to 8 and Comparative Examples 1 to 6 was applied to the polyester after the release treatment so as to have a dry thickness of 2 μm by using a coating bar. The film was air-dried at room temperature for 1 hour, and then dried at 80 ° C for 3 hours in a hot air dryer, followed by 120 ° (: 2 hours of drying) The ceramic green sheet was obtained. (Evaluation) (Evaluation of mechanical strength) The obtained ceramic green sheets were peeled off from the polyester film, and the state of the ceramic green sheets was observed and evaluated in the following two stages: 〇: not on the ceramic green sheets Fracture or breakage observed-22- 201144254 X : Although only slightly microscopically observed breakage or breakage (slice evaluation) From the polyethylene terephthalate, the ceramic embryo is cut to 60 mm X 5 0 The size of mm was placed at 20 ° C for 3 minutes, and the side of the sheet was observed with an optical microscope. It is evaluated in the following two stages. 〇: No warping of ceramic green sheets was observed X: Although only slightly microscopically observed, the evaluation of the warpage mechanical strength and the evaluation of the green sheets on the ceramic green sheets were as shown in Table 1. -23- 201144254 [Table 1] May OO 0 0 ο 0 〇〇0 〇ο 0 XX 擗m Forged mo 〇0 ο ο ο 〇0 XXXX 0 ο Zhao Lu 1 i film destroys the deer 壊 deer 壊 m壊壊m 擗诹ms 8 ss 8 s SS ss S with g δ •«e ο ΚΙ ?: s J5 ro s S LA <0 P: o P: f= Ρ: mm hop so § o ο ο so ο ο go 〇〇S 〇sd 8 s ο ο ο ο S ο 跋K) a Zhao? gSi ssss 芑o S oo ο ο δ ssss R a 〇> a 〇> CM S3 οό CM οό eg η <π soo ο ot£? Ο § os 〇〇soos Ο 9 1 ο m cvi CO m 1ι -L CM ± CO ± I ΙΑ -1 Ϊ 00 Λ ί Ϊ 2 1 UJ % I l I Έ I έ g 安〇. I 1 g 1 t 1 mi CSl C9 m Grip 10 (0 Bu S 00 i N CD Inch U) to 闺 辑 辑 镒镒镒 镒镒镒 镒镒 镒镒 镒镒 产业 产业 产业 产业 a Industrial Applicability: According to the present invention, it is possible to provide a machine with sufficient mechanical strength - 24- 201144254 degree and less warped ceramic green sheet ceramic slurry for slurry composition, ceramic green sheet and laminated ceramic capacitor.