201107375 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種液晶配向劑，係含有使烷氧矽烷聚 縮合所得到之聚矽氧烷；以及由前述液晶配向劑所得到之 液晶配向膜，以及具有該液晶配向膜之液晶顯示元件。 【先前技術】 近年來，在液晶顯示元件的顯示方式之中，垂直式（ VA )之液晶顯示元件，正被廣泛利用於大畫面液晶電視 或高精細度行動用途（數位相機或行動電話顯示部）等。 在VA式方面，已知有在TFT基板或彩色濾光基板形成用於 控制液晶的倒下方向之突起的MVA式（Multi Vertical Alignment)，或者在基板之ITO電極形成狹縫，藉由電場 控制液晶倒下方向的PVA式（Paterned Vertical Alignment )° 其他VA配向方式還有PSA式（Polymer susutained Alignment )。在V A式之中，P S A式是近年受到注目的技 術。此方式係在液晶中添加光聚合性化合物，製作液晶面 板後’施加電場，在液晶倒下的狀態對液晶面板照射UV 。藉此’聚合性化合物發生光聚合，液晶之配向方向被固 定化而發生預傾（pretilt )’反應速度提升。VA式係在構 成液晶面板單側電極製作狹縫，即使是在對向側之電極圖 案並未設置如MVA般的突起或如PVA般的狹縫之構造亦可 運作，其特長爲製造簡化或能夠得到優異的面板透過率。 -5- 201107375 (參照專利文獻1 ) 另一方面，以往所使用的聚醯亞胺等有機系之液晶配 向膜材料之外，同時還已知有無機系之液晶配向膜材料。 例如有文獻報告出使用含有四烷氧矽烷、三烷氧矽烷、醇 以及草酸的反應生成物之液晶配向劑組成物作爲塗佈型無 機系配向膜之材料，在液晶顯示元件之電極基板上形成垂 直配向性、耐熱性以及均勻性優異的液晶配向膜。（參照 專利文獻2 ) 另外，還有文獻報告出藉由使用含有四烷氧矽烷，特 定之三烷氧矽烷以及水的反應生成物與特定二醇醚系溶劑 之液晶配向劑組成物，形成防止顯示不良、長時間驅動後 殘像特性仍然良好的 '不會使液晶配向能力降低，且對光 及熱之電壓保持率下降量低的液晶配向膜。（參照專利文 獻3 ) 先前技術文獻 專利文獻 專利文獻1:日本特開2004-3 0206 1號公報 專利文獻2:日本特開平09-28 1 502號公報 專利文獻3:日本特開2005-250244號公報 【發明內容】 [發明所欲解決之課題] 以往’在PSA式液晶顯示元件之中，添加於液晶之聚合 性化合物之溶解性低，若添加量增加，則會有在低溫時析 -6- 201107375 出這樣的問題。另一方面’若聚合性化合物之添加量減少 ’則無法得到良好的配向狀態。另外，殘留於液晶中未反 應之聚合性化合物會成爲液晶中之雜質（污染），因此會 有使液晶顯示元件之信賴性降低這樣的問題。 本發明之課題提供一種液晶顯示元件用之液晶配向劑 ，即使在PSA式之液晶顯示元件之中聚合性化合物量少的 情況’甚至在使用並未添加聚合性化合物之液晶的情況， 皆可提升反應速度’能夠得到良好的配向狀態；由該液晶 配向劑所得到之液晶配向膜、以及具有該液晶配向膜之液 晶顯示元件。 [用於解決課題之方法] 本發明要旨爲以下所述。‘ [1 ] 一種液晶配向劑’其係含有使烷氧矽烷聚縮合所得 到之聚矽氧烷’該烷氧矽烷係含式（1 )所表示之烷氧矽 烷及式（2)所表示之烷氧矽烷， R'Si(OR2)3 ( 1 ) (R1表示可經氟原子取代、碳原子數8〜30之烴基，R2表 示碳原子數1〜5之烷基） R3Si(OR4)3 ( 2 ) (R3表示經丙烯酸基或甲基丙烯酸基取代之烷基、R4表示 碳原子數1〜5之烷基）。 [2]上述[1 ]所記載之液晶配向劑，其中聚矽氧烷係進 一步使含有下述式（3 )所表示之烷氧矽烷聚縮合所得到 201107375 之聚矽氧烷， (R5)nSi(OR6)4-n ( 3 ) (R5係氫原子，或可經雜原子、鹵素原子、胺基、環氧丙 氧基（glycidoxy)、酼基、異氰酸酯基或脲基取代之碳原 子數1〜16之烴基，R6表示碳原子數1〜5之烷基，η表示〇 〜3之整數）。 [3] 上述[1]或[2]所記載之液晶配向劑，其中前述式（ 1)所表示之烷氧矽烷，在式（1)中R1爲碳原子數8〜22 之烴基，R2爲甲基或乙基。 [4] 上述[1]〜[3]之任一者所記載之液晶配向劑，其中 前述式（2)所表示之烷氧矽烷係選自3 -丙烯醯氧基丙基 三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷、3-甲基 丙燃醯氧基丙基三甲氧基砂垸、3 -甲基丙嫌酿氧基丙基三 乙氧基矽烷所構成之群中至少一種。 [5] 上述[2]〜[4]之任一者所記載之液晶配向劑，其中 前述式（3)所表示之烷氧矽烷之R5係碳原子數1〜6之烴 基。 [6] 上述[2]〜[5]之任一者所記載之液晶配向劑，其中 前述式（3)所表示之烷氧矽烷係在式（3)中之η爲〇之四 院氧砂院。 [7] 上述[1]〜[4]之任一者所記載之液晶配向劑，其中 前述式（1)所表示之烷氧矽烷在全部烷氧矽烷中含有0.1 〜30莫耳％ ’且前述式（2)所表示之烷氧矽烷在全部烷氧 矽烷中含有3〜60莫耳％。 -8 - 201107375 [8]上述[2]〜[7]之任一者所記載之液晶配向劑，其中 前述式（3)所表示之烷氧矽烷在全部烷氧矽烷中含有1〇 〜9 6.9莫耳％。 [9 ]上述[1 ]〜[8 ]之任一者所記載之液晶配向劑，其中 聚矽氧烷之含量係以Si〇2換算濃度表示含有〇.5〜15質量％ 〇 [1 0 ] —種液晶配向膜’係將上述[丨]〜[9 ]之任一者所 記載之液晶配向劑塗佈於基板，經燒成所得。 [1 1 ] 一種液晶顯示元件’係具有上述[1 〇 ]所記載之液 晶配向膜。 [1 2 ] —種液晶顯示元件，係對於以塗佈上述[丨]〜[9 ] 之任一者所記載之液晶配向劑，經燒成之兩片基板夾持液 晶的液晶胞，在施加電壓的狀態照射UV。 [1 3 ] —種液晶顯示元件之製造方法，係以塗佈上述[j ] 〜[9 ]之任一者所記載之液晶配向劑，經燒成之兩片基板夾 持液晶，在施加電壓的狀態照射UV。 [發明之效果] 依據本發明之液晶配向劑，即使在P S A式之液晶顯示 元件之中，添加於液晶之聚合性化合物量少的情況，以及 在使用並未添加聚合性化合物之液晶的情況，皆可提升反 應速度，能夠得到良好的配向狀態之液晶顯示元件用之液 晶配向膜，以及可得到具有該液晶配向膜之液晶顯示元件 -9 - 201107375 【實施方式】 以下針對本發明作詳細說明。 本發明爲一種液晶配向劑，係含有使烷氧矽烷聚縮合 所得到之聚矽氧烷，該烷氧矽烷，係含式（1 )所表示之 烷氧矽烷及式（2)所表示之烷氧矽烷。 R1 Si(OR2)3 ( 1 ) (R1表示可經氟原子取代碳原子數8〜30之烴基，R2表示 碳原子數1〜5之烷基）。另外，在本說明書之中，「可取 代」意指「經取代或未經取代」。 R3Si(OR4)3 ( 2 ) (R3表示經丙烯酸基或甲基丙烯酸基取代之烷基、R4表示 碳數1〜5之烷基）。 [聚矽氧烷] 式（1)所表示之烷氧矽烷之R1 (以下亦稱爲特定有 機基），只要是可經氟取代之碳原子數爲8〜30(宜爲8〜 22，特佳爲1 〇〜22 )之烴基，而且具有使液晶垂直配向的 效果，則並未特別受到限定。就該等舉例而言，可列舉烷 基、氟烷基、烯基 '苯乙基、苯乙烯烷基、萘基、氟苯烷 基等。在該等之中，R1爲烷基或氟烷基之烷氧矽烷較爲廉 價，而且容易以市售品的形式取得，故爲適合。特別是， R1爲烷基之烷氧矽烷爲佳。本發明所使用的聚矽氧烷，亦 可具有多種該等特定有機基。 式（1)所表示之烷氧矽烷之R2爲碳原子數1〜5，宜 -10- 201107375 爲1〜3之烷基。較佳爲、R2爲甲基或乙基。 列舉如此的式（1 )所表示之烷氧矽烷之具 而並不受其限定。 可列舉例如辛基三甲氧基矽烷、辛基三乙氧 癸基三甲氧基矽烷、癸基三乙氧基矽烷、十二烷 基矽烷、十二烷基三乙氧基矽烷、十六烷基三甲 、十六烷基三乙氧基矽烷、十七烷基三甲氧基矽 烷基三乙氧基矽烷、十八烷基三甲氧基矽烷、十 乙氧基矽烷、十九烷基三甲氧基矽烷、十九烷基 矽烷、十一烷基三乙氧基矽烷、十一烷基三甲氧 21-二十二烯基三乙氧基矽烷、十三氟辛基三甲 、十三氟辛基三乙氧基矽烷、十七氟癸基三甲氧 十七氟癸基三乙氧基矽烷、異辛基三乙氧基矽烷 三乙氧基矽烷、五氟苯基丙基三甲氧基矽烷、（ 乙氧基矽烷、（1-萘）三甲氧基矽烷等。在其中 基三甲氧基矽烷、辛基三乙氧基矽烷、癸基三甲 、癸基三乙氧基矽烷、十二烷基三甲氧基矽烷、 三乙氧基矽烷、十六烷基三甲氧基矽烷、十六烷 基矽烷、十七烷基三甲氧基矽烷、十七烷基三乙 、十八院基二甲氧基砂院、十八垸基三乙氧基砂 烷基三甲氧基矽烷、十九烷基三乙氧基矽烷、十 乙氧基矽烷、或十一烷基三甲氧基矽烷爲佳。 爲了得到良好的液晶配向性，具有上述特定 式（1 )所表示之烷氧矽烷，係以在爲了得到聚 體例，然 基矽烷、 基三甲氧 氧基矽烷 烷、十七 八烷基三 三乙氧基 基矽烷、 氧基矽烷 基矽烷、 、苯乙基 1-萘）三 尤其以辛 氧基砂院 十二烷基 基三乙氧 氧基矽烷 烷、十九 一院基三 有機基之 矽氧烷所 -11 - 201107375 使用之全部院氧矽烷中含^丨莫耳^以上爲佳。較佳爲〇 5 莫耳％以上。更佳爲1莫耳％以上。另外，爲了使所形成之 液晶配向膜得到充足的硬化特性，係以3 0莫耳％以下爲佳 。較佳爲22莫耳％以下。 另一方面’式（2)所表示之烷氧矽烷之r3(以下亦 稱爲第二特定有機基），R3係經丙烯酸基或甲基丙烯酸基 取代之烷基。被取代的氫原子爲一個以上，宜爲一個。烷 基之碳原子數係以1〜30爲佳，較佳爲1〜10。更佳爲5 。式（2)所表示之烷氧矽烷之R4係與上述式（1)中。之 定義相同’另外’ R4所適合的基亦與R2之情況相同。 列舉式（2)所表示之烷氧矽烷之具體例，然而並不 受到該等限定。可列舉例如3 -甲基丙烯醯氧基丙基三甲氧 基矽烷、3 -甲基丙烯醯氧基丙基三乙氧基矽烷、甲基丙烯 醯氧基甲基三甲氧基矽烷、甲基丙烯醯氧基甲基三乙氧基 矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3_丙烯醯氧基丙 基三乙氧基矽烷、丙烯醯氧基乙基三甲氧基矽烷、丙烯醯 氧基乙基三乙氧基矽烷等。 即使是在P S A式之聚合性化合物少的情況，爲了提升 PSA式液晶顯示元件之反應速度，具有第二特定有機基之 式（2 )所表示之烷氧矽烷，係以在爲了得到聚矽氧烷所 使用之全部烷氧矽烷中含3莫耳％以上爲佳。較佳爲5莫耳 %以上。更佳爲1 0莫耳％以上。另外，爲了使所形成的液 晶配向膜充分硬化，係以60莫耳％以下爲佳。 在本發明中，式（1)所表示之烷氧矽烷宜爲在所使 -12- 201107375 用之全部烷氧矽烷中含有0.1〜30莫耳％，特佳爲2〜2〇莫 耳％，且式（2 )所表示之烷氧矽烷係以在所使用的全部烷 氧矽烷中含有3〜60莫耳％爲佳’特佳爲5〜30莫耳％。 在本發明中’除了式（1)及式（2)所表示之烷氧矽 烷以外，還可使用下述式（3)所表示之烷氧矽烷。式（3 )所表示之烷氧矽烷，由於可對聚矽氧烷賦予各種之特性 ，因此可因應必要特性而選擇使用一種或多種。 (R5)nSi(OR6)4.n ( 3 ) 式中’ R5係氫原子，或可經雜原子、鹵素原子 '胺基 、環氧丙氧基、锍基、異氰酸酯基或脲基取代之碳原子數 1〜6之烴基，R6係碳原子數1〜5 (宜爲1〜3)之院基，n 表示0〜3(宜爲0〜2)之整數。 式（3)所表示之烷氧矽烷之R5係氫原子，或碳原子 數爲1〜6之有機基（以下亦稱爲第三有機基）。就第三有 機基的例子而言，脂肪族烴；如脂肪族環、芳香族環以及 雜環般的環構造；不飽和鍵；以及可含氧原子、氮原子、 硫原子等雜原子等而且可具有分支構造之碳原子數爲1〜 1 6 (較佳爲1〜1 2，特佳爲1〜6 )之烴。該烴可經鹵素原 子、胺基、環氧丙氧基、锍基、異氰酸酯基、脲基等取代 〇 列舉如此的式（3 )所表示之烷氧矽烷之具體例，然 而並不受其限定。 在式（3)之烷氧矽烷中之R5爲氫原子的情況下，就 烷氧矽烷之具體例而言，可列舉三甲氧基矽烷、三乙氧基 -13- 201107375 矽烷、三丙氧基矽烷、三丁氧基矽烷等。 另外，在式（3)之烷氧矽烷中之R5爲第三有機基之 情況下，烷氧矽烷之具體例而言，可列舉甲基三甲氧基矽 烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧 基矽烷、丙基三甲氧基矽烷、丙基三乙氧基矽烷、甲基三 丙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙 氧基矽烷、N-2 (胺基乙基）3-胺基丙基三乙氧基矽烷、 N-2 (胺基乙基）3-胺基丙基三甲氧基矽烷、3-(2-胺基乙 基胺基丙基）三甲氧基矽烷、3-(2 -胺基乙基胺基丙基） 三乙氧基矽烷、2-胺基乙基胺基甲基三甲氧基矽烷、2-( 2 -胺基乙基硫乙基）三乙氧基矽烷、3 -巯基丙基三乙氧基 矽烷、锍基甲基三甲氧基矽烷、3 -異氰酸酯丙基三乙氧基 矽烷、三氟丙基三甲氧基矽烷、氯丙基三乙氧基矽烷、溴 丙基三乙氧基矽烷、3 -锍基丙基三甲氧基矽烷、二甲基二 乙氧基矽烷、二甲基二甲氧基矽烷、二乙基二乙氧基矽烷 、二乙基二甲氧基矽烷、二苯二甲氧基矽烷、二苯二乙氧 基矽烷、3-胺基丙基甲基二乙氧基矽烷、3-胺基丙基二甲 基乙氧基矽烷、三甲基乙氧基矽烷、三甲基甲氧基矽烷、 7 -脲丙基三乙氧基矽烷、r-脲丙基三甲氧基矽烷以及7-脲丙基三丙氧基矽烷等。 本發明所使用之聚矽氧烷，係以改善與基板之密著性 、與液晶分子之親和性等爲目的，只要是在不損及本發明 之效果的情況’可具有一種或多種上述式（3)所表示之 烷氧矽烷。 -14- 201107375 在式（3)所表示之烷氧矽烷中之n爲〇之烷氧矽烷， 係四烷氧矽烷。四烷氧矽烷由於容易與式（1)及式（2) 所表示之烷氧矽烷縮合，故爲了得到本發明之聚矽氧烷而 爲適合。 就如此的式（3)中之η爲0之烷氧矽烷而言，係以四 甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷或四丁氧基矽 烷爲較佳，特別是，四甲氧基矽烷或四乙氧基矽烷爲佳。 在倂用式（3 )所表示之烷氧矽烷的情況下，式（3 ) 所表示之烷氧矽烷之使用量，係以爲了得到聚矽氧烷所使 用之全部烷氧矽烷中含10〜96.9莫耳％爲佳。較佳爲35〜 9 9.8莫耳％。 [聚矽氧烷之製造方法] 得到本發明所使用之聚矽氧烷之方法，並未特別受到 限定。在本發明中，係使上述式（1 )及式（2 )爲必須成 分之烷氧矽烷在有機溶劑中縮合而得到。通常聚矽氧烷， 係使如此的烷氧矽烷聚縮合，以均勻溶解於有機溶劑之溶 液的形式得到。 就使上述烷氧矽烷聚縮合之方法而言，可列舉例如使 烷氧矽烷在醇或二醇等溶劑中水解、縮合之方法。此時， 水解、縮合反應爲部分水解以及完全水解之任一者皆可》 在完全水解之情況，理論上只要加入烷氧矽烷中全部烷氧 基之0.5倍莫耳數之水即可，而通常以加入過剩於〇.5倍莫 耳數之水量爲佳。 -15- 201107375 上述反應所使用之水量，可依照希望而適當地選擇， 而通常以烷氧矽烷中之全部烷氧基之0.5〜2·5倍莫耳數爲 佳。 另外，在本發明中，通常爲了促進水解、縮合反應之 目的，係以使用鹽酸、硫酸、硝酸、醋酸、蟻酸、草酸、 馬來酸、富馬酸等酸；氨、甲胺、乙胺、乙醇胺、三乙胺 等鹼；鹽酸、硫酸、硝酸等金屬鹽；等觸媒爲佳。另外， 還可藉著將溶解有烷氧矽烷的溶液加熱，進一步促進水解 、縮合反應。此時，加熱溫度以及加熱時間可依照希望而 適當選擇。可列舉例如在5 0 °C加熱、攪拌2 4小時，在回流 下加熱、攪拌1小時等方法。 另外，就其他方法而言，可列舉例如將烷氧矽烷、溶 劑以及草酸之混合物加熱而聚縮合之方法。具體而言，預 先在醇中加入草酸製成草酸醇溶液之後，在將該溶液加熱 的狀態下混合烷氧矽烷之方法。此時所使用之草酸量，係 以定爲相對於烷氧矽烷所具有全部烷氧基之1莫耳而言的 0.2〜2莫耳爲佳。此方法中之加熱，可在液溫50〜180 °C 進行。宜爲以液體不會發生蒸散、揮發等的方式，在回流 之下加熱數十分鐘至十數小時之方法。 在得到聚矽氧烷時，使用多種烷氧矽烷之情況下，可 預先混合烷氧矽烷，亦可依序混合多種烷氧矽烷。 使烷氧矽烷聚縮合時所使用之溶劑（以下亦稱爲聚合 溶劑）’只要是能溶解烷氧矽烷的物質，則並未特別受到 限定。另外，即使烷氧矽烷未溶解之情況，只要會隨著烷 -16- 201107375 氧矽烷聚縮合反應之進行而溶解即可。一般而言，由於烷 氧矽烷之聚縮合反應會產生醇，因此可使用醇類、二醇類 、二醇醚類、或與醇類相溶性良好的有機溶劑。 就如此的聚合溶劑之具體例而言，可列舉甲醇、乙醇 、丙醇、丁醇、二丙酮醇等醇類；乙二醇、二乙二醇、丙 二醇、二丙二醇、己二醇、1，3-丙二醇、1，2-丁二醇、1，3-丁 二醇、1，4-丁 二醇、2,3-丁 二醇、1,2-戊二醇、1，3-戊二 醇、1,4-戊二醇、1,5-戊二醇、2,4-戊二醇、2,3-戊二醇、 1,6-己二醇等二醇類：乙二醇單甲醚' 乙二醇單乙醚、乙 二醇單丙醚、乙二醇單丁醚、乙二醇二甲醚、乙二醇二乙 醚、乙二醇二丙醚、乙二醇二丁醚、二乙二醇單甲醚、二 乙二醇單乙醚、二乙二醇單丙醚、二乙二醇單丁醚、二乙 二醇二甲醚、二乙二醇二乙醚、二乙二醇二丙醚、二乙二 醇二丁醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚 、丙二醇單丁醚、丙二醇二甲醚、丙二醇二乙醚' 丙二醇 二丙醚、丙二醇二丁醚等二醇醚類、N -甲基-2-吡咯烷酮 、N，N -二甲基甲醯胺、N，N-二甲基乙醯胺、7··丁內酯、 二甲亞颯、四甲基尿素 '六甲基磷三醯胺、間甲酚等。 在本發明中，亦可將上述聚合溶劑混合多種而使用。 上述方法所得到之聚矽氧烷之聚合溶液（以下亦稱爲 聚合溶液），宜將作爲原料所裝入全部烷氧矽烷之矽原子 換算爲Si〇2的濃度（以下稱爲Si〇2換算濃度）定爲20質量 %以下，進一步以定爲5〜1 5質量％爲較佳。在此濃度範圍 之中可任意選擇濃度，而藉此能夠抑制膠體生成而得到均 -17- 201107375 質的溶液。 [聚矽氧烷之溶液] 在本發明中，可將上述方法所得到之聚合溶液直接製 成聚矽氧烷之溶液，亦可因應必要將上述方法所得到之溶 液加以濃縮、加入溶劑而進行稀釋’或以其他溶劑取代而 製成聚矽氧烷之溶液。 此時，所使用之溶劑（以下亦稱爲添加溶劑）’可與 聚合溶劑相同，亦可採用其他溶劑。此添加溶劑只要能使 聚矽氧烷均勻溶解，則並未特別受到限定，可任意選擇— 種或多種使用。 就如此的添加溶劑之具體例而言，除了上述聚合溶劑 舉例之溶劑以外，還可列舉丙酮、甲基乙基酮、甲基異丁 基酮等酮類；醋酸甲酯、醋酸乙酯、乳酸乙酯等酯類。 該等溶劑可調整液晶配向劑之黏度，或在藉著旋轉塗 佈、膠版印刷、噴墨等將液晶配向劑塗佈於基板上時使塗 佈性提升。 [其他成分] 在本發明之液晶配向劑之中，只要不損及本發明之效 果，亦可含聚矽氧烷以外之其他成分，例如無機微粒子、 金屬氧院（Metalloxane)寡聚物、金屬氧院聚合物、均勻 劑，甚至界面活性劑等成分。 就無機微粒子而言，係以二氧化矽微粒子、氧化鋁微 -18- 201107375 粒子、二氧化鈦微粒子、或氟化鎂微粒子 尤其以膠體溶液之狀態爲佳。此膠體溶液 子分散於分散媒而得者，或者亦可爲市售 在本發明中，藉由含有無機微粒子，可對 膜賦予表面形狀以及其他機能。就無機微 其平均粒徑爲0.001〜〇.2μπι爲佳，更佳爲 在無機微粒子之平均粒徑超過0.2 μιη之情 製之塗佈液而形成的硬化被膜，會有透明 就無機微粒子之分散媒而言，可列舉 。就膠體溶液而言，從被膜形成用塗佈液 看來，係以pH或pKa調整爲1〜10爲佳。較 就膠體溶液之分散媒所使用之有機溶 甲醇、丙醇、丁醇、乙二醇、丙二醇、丁 己二醇、二乙二醇、二丙二醇、乙二醇單 基乙基酮、甲基異丁基酮等酮類；甲苯、 烴類；二甲基甲醯胺、二甲基乙醯胺、N-醯胺類；醋酸乙酯、醋酸丁酯、r-丁內 呋喃、I，4-二噁烷等醚類。在該等之中， 佳。該等有機溶劑，可單獨或混合兩種以 的形式使用。 就金屬氧烷寡聚物、金屬氧烷聚合物 、鈦、鋁、鉬、銻、鉍、錫、銦、鋅等單 前驅物。就金屬氧烷寡聚物、金屬氧烷聚 售品或者由金屬烷氧化物、硝酸鹽、鹽酸 等微粒子爲佳， ，係使無機微粒 品之膠體溶液。 所形成的硬化被 粒子而言，係以 0.001 〜Ο.ίμιη 〇 況下，使用所調 性降低之情況》 水以及有機溶劑 之安定性之觀點 佳爲2〜7。 劑而言，可列舉 二醇、戊二醇、 丙醚等醇類：甲 二甲苯等芳香族 •甲基吡咯烷酮等 酯等酯類；四氫 以醇類或酮類爲 上，而以分散媒 而言，可使用矽 獨或複合氧化物 合物而言，爲市 鹽、羧酸鹽等單 -19- 201107375 體，藉由水解等常法所得到者皆可。 就市售品之金屬氧院寡聚物、金屬氧院聚合物之具體 例而言’可列舉Colcoat公司製之Methylsilicate 51、201107375 6. Technical Field of the Invention The present invention relates to a liquid crystal alignment agent comprising a polyoxyalkylene obtained by polycondensing an alkoxysilane; and a liquid crystal alignment film obtained by the liquid crystal alignment agent. And a liquid crystal display element having the liquid crystal alignment film. [Prior Art] In recent years, among liquid crystal display elements, vertical (VA) liquid crystal display elements are being widely used for large-screen LCD TVs or high-definition mobile applications (digital cameras or mobile phone display units). )Wait. In the VA type, it is known to form a MVA type (Multi Vertical Alignment) for controlling a protrusion in a falling direction of a liquid crystal on a TFT substrate or a color filter substrate, or to form a slit in an ITO electrode of a substrate, which is controlled by an electric field. PVA type (Paterned Vertical Alignment) in the liquid crystal falling direction. Other VA alignment methods include PSA type (Polymer susutained Alignment). Among the V A formulas, the P S A type is a technique that has attracted attention in recent years. In this method, a photopolymerizable compound is added to the liquid crystal, and after the liquid crystal panel is produced, an electric field is applied, and the liquid crystal panel is irradiated with UV in a state where the liquid crystal falls. Thereby, the polymerizable compound undergoes photopolymerization, and the alignment direction of the liquid crystal is fixed, and the pretilt' reaction rate is increased. In the VA type, a slit is formed in one side electrode of the liquid crystal panel, and even if the electrode pattern on the opposite side is not provided with a protrusion like MVA or a slit like PVA, the function is simplified or Excellent panel transmittance can be obtained. -5-201107375 (refer to Patent Document 1) On the other hand, an organic liquid crystal alignment film material is known in addition to an organic liquid crystal alignment film material such as polyimide. For example, it has been reported in the literature that a liquid crystal alignment agent composition containing a reaction product of a tetraalkanoxane, a trialkoxide, an alcohol, and an oxalic acid is used as a material of a coating type inorganic alignment film, and is formed on an electrode substrate of a liquid crystal display element. A liquid crystal alignment film excellent in vertical alignment, heat resistance, and uniformity. (Refer to Patent Document 2) Further, it has been reported in the literature to prevent formation by using a liquid crystal alignment agent composition containing a reaction product of a tetraalkanoxane, a specific trialkoxysilane, and water and a specific glycol ether solvent. A liquid crystal alignment film which does not cause a decrease in liquid crystal alignment ability and has a low voltage retention rate of light and heat, which exhibits poor after-image characteristics after long-term driving. (Patent Document 3) PRIOR ART DOCUMENT Patent Document Patent Document 1: JP-A-2004-3 0206 No. 1 Patent Document 2: Japanese Patent Laid-Open No. 09-28 No. 502 Patent Document 3: Japanese Patent Laid-Open No. 2005-250244 [Invention] [Problems to be Solved by the Invention] Conventionally, in a PSA liquid crystal display device, the solubility of a polymerizable compound added to a liquid crystal is low, and when the amount of addition is increased, it is precipitated at a low temperature. - 201107375 This is the problem. On the other hand, when the amount of the polymerizable compound added is reduced, a good alignment state cannot be obtained. Further, since the polymerizable compound which is not reacted in the liquid crystal becomes an impurity (contamination) in the liquid crystal, there is a problem that the reliability of the liquid crystal display element is lowered. An object of the present invention is to provide a liquid crystal alignment agent for a liquid crystal display device, which can be improved even when a liquid crystal display element is used in a liquid crystal display element of a PSA type, even when a liquid crystal in which a polymerizable compound is not added is used. The reaction rate 'is a good alignment state; a liquid crystal alignment film obtained from the liquid crystal alignment agent; and a liquid crystal display element having the liquid crystal alignment film. [Method for Solving the Problem] The gist of the present invention is as follows. ' [1] A liquid crystal alignment agent which contains a polyoxyalkylene obtained by polycondensation of an alkoxysilane. The alkoxysilane is an alkoxysilane represented by the formula (1) and represented by the formula (2). Alkoxydecane, R'Si(OR2)3 (1) (R1 represents a hydrocarbon group which may be substituted by a fluorine atom and has 8 to 30 carbon atoms, and R2 represents an alkyl group having 1 to 5 carbon atoms) R3Si(OR4)3 ( 2) (R3 represents an alkyl group substituted with an acryl group or a methacryl group, and R4 represents an alkyl group having 1 to 5 carbon atoms). [2] The liquid crystal alignment agent according to the above [1], wherein the polyoxyalkylene is further obtained by polycondensation of an alkoxysilane represented by the following formula (3) to obtain a polyoxane of 201107375, (R5)nSi. (OR6)4-n ( 3 ) (R5 is a hydrogen atom or a carbon atom which may be substituted by a hetero atom, a halogen atom, an amine group, a glycidoxy group, a decyl group, an isocyanate group or a ureido group; A hydrocarbon group of ～16, R6 represents an alkyl group having 1 to 5 carbon atoms, and η represents an integer of 〇3 to 3). [3] The liquid crystal alignment agent according to the above [1], wherein the alkoxy oxane represented by the above formula (1), in the formula (1), R1 is a hydrocarbon group having 8 to 22 carbon atoms, and R2 is Methyl or ethyl. [4] The liquid crystal alignment agent according to any one of the above [1], wherein the alkoxysilane represented by the formula (2) is selected from the group consisting of 3-propenyloxypropyltrimethoxydecane. 3-propenyloxypropyltriethoxydecane, 3-methylpropenyloxypropyltrimethoxysilane, 3-methylpropionoxypropyltriethoxydecane At least one of the groups. [5] The liquid crystal alignment agent according to any one of the above [2], wherein the alkoxysilane represented by the formula (3) is a hydrocarbon group having 1 to 6 carbon atoms. [6] The liquid crystal alignment agent according to any one of the above [2], wherein the alkoxy decane represented by the formula (3) is a sulphur oxide of the fourth courtyard of the formula (3) hospital. [7] The liquid crystal alignment agent according to any one of the above [1], wherein the alkoxydecane represented by the formula (1) contains 0.1 to 30 mol% of the total alkoxysilane and the aforementioned The alkoxydecane represented by the formula (2) contains 3 to 60 mol% of the total alkoxysilane. The liquid crystal alignment agent of any one of the above-mentioned [2], wherein the alkoxy oxane represented by the above formula (3) contains 1 〇 to 9 6.9 of all alkoxy decane. Moer%. [9] The liquid crystal alignment agent according to any one of the above [1] to [8], wherein the content of the polyoxyalkylene is contained in an amount of 〇.5 to 15% by mass in terms of concentration in terms of Si〇2 〇[1 0 ] In the liquid crystal alignment film, the liquid crystal alignment agent described in any one of the above [丨] to [9] is applied onto a substrate and fired. [1 1 ] A liquid crystal display element ’ has the liquid crystal alignment film described in the above [1 〇 ]. [1 2] A liquid crystal display device in which a liquid crystal cell in which liquid crystal is sandwiched between two substrates which are fired by applying the liquid crystal alignment agent described in any one of the above [丨] to [9] is applied. The state of the voltage illuminates the UV. [1] A method for producing a liquid crystal display device, wherein the liquid crystal alignment agent described in any one of [j] to [9] is applied, and the liquid crystal is sandwiched between the two substrates which are fired, and a voltage is applied thereto. The state illuminates the UV. [Effects of the Invention] The liquid crystal alignment agent of the present invention has a small amount of a polymerizable compound added to a liquid crystal, and a liquid crystal in which a polymerizable compound is not added, even in a PSA type liquid crystal display device. A liquid crystal alignment film for a liquid crystal display element having a good alignment state can be obtained, and a liquid crystal display element having the liquid crystal alignment film can be obtained. -9 - 201107375 [Embodiment] Hereinafter, the present invention will be described in detail. The present invention relates to a liquid crystal alignment agent comprising a polyoxyalkylene obtained by polycondensing an alkoxysilane, which comprises an alkoxysilane represented by the formula (1) and an alkane represented by the formula (2). Oxane. R1 Si(OR2)3 ( 1 ) (R1 represents a hydrocarbon group having 8 to 30 carbon atoms which may be substituted by a fluorine atom, and R2 represents an alkyl group having 1 to 5 carbon atoms). In addition, in the present specification, "replaceable" means "substituted or unsubstituted". R3Si(OR4)3(2) (R3 represents an alkyl group substituted with an acryl group or a methacryl group, and R4 represents an alkyl group having 1 to 5 carbon atoms). [polyoxyalkylene] R1 (hereinafter also referred to as a specific organic group) of the alkoxysilane represented by the formula (1), as long as it is a fluorine atom-substituted carbon atom number of 8 to 30 (preferably 8 to 22, It is preferably a hydrocarbon group of 1 〇 to 22) and has an effect of vertically aligning the liquid crystal, and is not particularly limited. Examples thereof include an alkyl group, a fluoroalkyl group, an alkenyl group, a phenethyl group, a styrene group, a naphthyl group, a fluorophenyl group, and the like. Among these, an alkoxysilane wherein R1 is an alkyl group or a fluoroalkyl group is relatively inexpensive, and is easily obtained as a commercially available product, and is therefore suitable. In particular, it is preferred that R1 is an alkyl alkane. The polyoxyalkylene used in the present invention may also have a plurality of such specific organic groups. R2 of the alkoxydecane represented by the formula (1) is an alkyl group having 1 to 5 carbon atoms, preferably -10-201107375. Preferably, R2 is a methyl group or an ethyl group. The alkoxysilane represented by the formula (1) is exemplified and is not limited thereto. For example, octyltrimethoxydecane, octyltriethoxydecyltrimethoxydecane, decyltriethoxydecane, dodecyldecane, dodecyltriethoxydecane, cetyl group Trimethyl, hexadecyltriethoxydecane, heptadecyltrimethoxydecyltriethoxydecane,octadecyltrimethoxydecane,decaethoxydecane,dodecyltrimethoxydecane , nonadecane decane, undecyltriethoxy decane, undecyltrimethoxy 21-icosadienyltriethoxy decane, tridecafluorooctyltrimethyl, tridecafluorooctyltriethyl Oxydecane, heptadecafluorodecyltrimethoxyheptadecafluorodecyltriethoxydecane, isooctyltriethoxydecanetriethoxydecane, pentafluorophenylpropyltrimethoxydecane, (ethoxy A decyl, a (1-naphthalene) trimethoxy decane, etc., wherein a tributyl methoxy decane, an octyl triethoxy decane, a decyltrimethyl, a decyl triethoxy decane, a dodecyl trimethoxy decane , triethoxydecane, cetyltrimethoxydecane, cetyldecane, heptadecyltrimethoxydecane, ten Alkyl triethyl, 18-yard dimethoxy sand, 18 decyl triethoxy sand alkyl trimethoxy decane, nineteen alkyl triethoxy decane, decaethoxy decane, or ten The monoalkyltrimethoxydecane is preferred. In order to obtain good liquid crystal alignment, the alkoxysilane represented by the above specific formula (1) is used in order to obtain a polymer, a decyl, a methoxymethoxydecane. Alkane, heptadecyltritriethoxydecane, oxydecylalkylnonane, phenethyl 1-naphthalene) III, especially octyloxylate ladodecyltriethoxyoxydecane, Nineteenth hospital base triorgano-based oxane -11 - 201107375 All the oxoxane used in the hospital contains ^ 丨 Mo ^ ^ is better. It is preferably 〇 5 mol% or more. More preferably, it is 1 mol% or more. Further, in order to obtain sufficient hardening characteristics of the formed liquid crystal alignment film, it is preferably 30% by mole or less. It is preferably 22 mol% or less. On the other hand, r3 of an alkoxysilane represented by the formula (2) (hereinafter also referred to as a second specific organic group), and R3 is an alkyl group substituted with an acryl group or a methacryl group. The number of hydrogen atoms to be substituted is one or more, and it is preferably one. The number of carbon atoms of the alkyl group is preferably from 1 to 30, preferably from 1 to 10. More preferably 5 . The R4 system of the alkoxydecane represented by the formula (2) is in the above formula (1). The definition is the same as 'other'. The base suitable for R4 is also the same as in the case of R2. Specific examples of the alkoxysilane represented by the formula (2) are not limited thereto. For example, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, methacryloxymethyltrimethoxydecane, and methacryl醯oxymethyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propyleneoxypropyltriethoxydecane, propyleneoxyethyltrimethoxydecane, propylene Alkoxyethyltriethoxydecane, and the like. In the case where the number of polymerizable compounds of the PSA type is small, in order to increase the reaction rate of the PSA type liquid crystal display element, the alkoxysilane represented by the formula (2) having the second specific organic group is used in order to obtain polyoxyl It is preferred that all of the alkoxysilanes used in the alkane contain 3 mol% or more. It is preferably 5 mol% or more. More preferably, it is more than 10% by mole. Further, in order to sufficiently harden the formed liquid crystal alignment film, it is preferably 60 mol% or less. In the present invention, the alkoxysilane represented by the formula (1) is preferably contained in an amount of from 0.1 to 30 mol%, particularly preferably from 2 to 2 mol%, based on the total alkoxydecane used in the period of -12 to 201107375. Further, the alkoxysilane represented by the formula (2) is preferably from 3 to 60 mol%, more preferably from 5 to 30 mol%, based on all the alkoxysilanes used. In the present invention, in addition to the alkoxysilane represented by the formula (1) and the formula (2), an alkoxysilane represented by the following formula (3) can be used. Since the alkoxysilane represented by the formula (3) imparts various properties to the polyoxyalkylene, one or more kinds may be selected depending on the necessary properties. (R5)nSi(OR6)4.n ( 3 ) where R 5 is a hydrogen atom or a carbon which may be substituted with a hetero atom, a halogen atom 'amine group, a glycidoxy group, a decyl group, an isocyanate group or a urea group a hydrocarbon group having 1 to 6 atomic numbers, R6 is a hospital group having 1 to 5 carbon atoms (preferably 1 to 3), and n is an integer of 0 to 3 (preferably 0 to 2). The R5 hydrogen atom of the alkoxysilane represented by the formula (3) or an organic group having 1 to 6 carbon atoms (hereinafter also referred to as a third organic group). In the case of the third organic group, an aliphatic hydrocarbon; an aliphatic ring, an aromatic ring, and a heterocyclic ring structure; an unsaturated bond; and a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom, etc. A hydrocarbon having a branched structure of 1 to 16 (preferably 1 to 12, particularly preferably 1 to 6). The hydrocarbon may be substituted by a halogen atom, an amine group, a glycidoxy group, a decyl group, an isocyanate group, a ureido group or the like. Specific examples of the alkoxysilane represented by the formula (3) are exemplified, but are not limited thereto. . In the case where R5 in the alkoxysilane of the formula (3) is a hydrogen atom, specific examples of the alkoxydecane include trimethoxydecane, triethoxy-13-201107375 decane, and tripropoxy group. Decane, tributoxydecane, and the like. Further, in the case where R5 in the alkoxysilane of the formula (3) is the third organic group, specific examples of the alkoxydecane include methyltrimethoxydecane, methyltriethoxydecane, and B. Trimethoxy decane, ethyl triethoxy decane, propyl trimethoxy decane, propyl triethoxy decane, methyl tripropoxy decane, 3-aminopropyl trimethoxy decane, 3- Aminopropyltriethoxydecane, N-2 (aminoethyl) 3-aminopropyltriethoxydecane, N-2 (aminoethyl) 3-aminopropyltrimethoxydecane , 3-(2-Aminoethylaminopropyl)trimethoxynonane, 3-(2-aminoethylaminopropyl)triethoxydecane, 2-aminoethylaminomethyl Trimethoxy decane, 2-(2-aminoethylthioethyl)triethoxydecane, 3-mercaptopropyltriethoxydecane, decylmethyltrimethoxydecane, 3-isocyanatepropyltri Ethoxy decane, trifluoropropyltrimethoxydecane, chloropropyltriethoxydecane, bromopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, dimethyldiethoxy Decane, dimethyldimethoxyanthracene , diethyldiethoxydecane, diethyldimethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, 3-aminopropylmethyldiethoxydecane, 3 - aminopropyl dimethyl ethoxy decane, trimethyl ethoxy decane, trimethyl methoxy decane, 7 - urea propyl triethoxy decane, r - urea propyl trimethoxy decane 7-ureidopropylpropoxydecane, and the like. The polyoxyalkylene used in the present invention is intended to improve the adhesion to the substrate, the affinity with the liquid crystal molecules, and the like, and may have one or more of the above formulas as long as the effects of the present invention are not impaired. (3) The alkoxy decane represented. -14- 201107375 In the alkoxysilane represented by the formula (3), n is an alkoxysilane of hydrazine, which is a tetraalkane. Since the tetraalkane is easily condensed with the alkoxysilane represented by the formula (1) and the formula (2), it is suitable for obtaining the polyoxyalkylene of the present invention. In the case of the alkoxy decane wherein η is 0 in the formula (3), tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane or tetrabutoxy decane is preferred, in particular Preferably, tetramethoxy decane or tetraethoxy decane is used. In the case of using the alkoxysilane represented by the formula (3), the alkoxynonane represented by the formula (3) is used in an amount of 10 to 10% of all alkoxysilanes used for obtaining the polyoxyalkylene. 96.9% of the mole is better. It is preferably 35 to 9 9.8 mol%. [Method for Producing Polyoxane] The method for obtaining the polyoxyalkylene used in the present invention is not particularly limited. In the present invention, the above formula (1) and formula (2) are obtained by condensing an alkoxysilane having a necessary component in an organic solvent. Usually, polyoxyalkylene is obtained by polycondensation of such alkoxysilane in the form of a solution uniformly dissolved in an organic solvent. The method for polycondensing the above alkoxydecane may, for example, be a method of hydrolyzing and condensing alkoxysilane in a solvent such as an alcohol or a diol. In this case, the hydrolysis and the condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add water of 0.5 times the molar amount of all alkoxy groups in the alkoxysilane. It is usually preferred to add water in excess of 55 times the number of moles. -15- 201107375 The amount of water used in the above reaction can be appropriately selected as desired, and it is usually 0.5 to 2.5 times the number of moles of all alkoxy groups in the alkoxysilane. Further, in the present invention, in order to promote the hydrolysis and condensation reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid is used; ammonia, methylamine, ethylamine, A base such as ethanolamine or triethylamine; a metal salt such as hydrochloric acid, sulfuric acid or nitric acid; and the like is preferred. Further, the hydrolysis and condensation reaction can be further promoted by heating a solution in which the alkoxysilane is dissolved. At this time, the heating temperature and the heating time can be appropriately selected as desired. For example, a method of heating and stirring at 50 ° C for 24 hours, heating under reflux, and stirring for 1 hour can be mentioned. Further, as another method, for example, a method in which a mixture of alkoxysilane, a solvent, and oxalic acid is heated and condensed is mentioned. Specifically, a method of mixing an alkoxysilane in a state where the solution is heated by adding oxalic acid to an alcohol to prepare an oxalic acid alcohol solution. The amount of oxalic acid used at this time is preferably 0.2 to 2 moles per 1 mole of the alkoxy group having alkoxysilane. The heating in this method can be carried out at a liquid temperature of 50 to 180 °C. It is preferred to heat the liquid under reflux for several tens of minutes to ten hours in such a manner that the liquid does not evaporate or volatilize. In the case of using a polyoxoxane, a plurality of alkoxysilanes may be used, and the alkoxysilane may be mixed in advance, or a plurality of alkoxysilanes may be sequentially mixed. The solvent (hereinafter also referred to as a polymerization solvent) used in the polycondensation of the alkoxydecane is not particularly limited as long as it is a substance capable of dissolving the alkoxysilane. Further, even if the alkoxysilane is not dissolved, it may be dissolved as the alkane-16-07307375 oxane condensation polymerization proceeds. In general, since an alcohol is produced by a polycondensation reaction of alkoxysilane, an alcohol, a glycol, a glycol ether, or an organic solvent having good compatibility with an alcohol can be used. Specific examples of such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone alcohol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and hexanediol; 3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentane Alcohols, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol, etc. Methyl ether 'ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether 'propylene glycol dipropyl ether, propylene glycol dibutyl ether, etc. Glycol ethers, N-methyl-2-pyrrolidone, N,N-dimethylformamidine , N, N- dimethylacetamide, butyrolactone ·· 7, Sa dimethylsulfoxide, tetramethylurea 'Amides hexamethylphosphoric triamide, m-cresol and the like. In the present invention, a plurality of the above polymerization solvents may be used in combination. The polymerization solution of the polyoxyalkylene obtained by the above method (hereinafter also referred to as a polymerization solution) is preferably converted into a concentration of Si〇2 in terms of a ruthenium atom in which all alkoxysilanes are charged as a raw material (hereinafter referred to as Si〇2 conversion). The concentration is preferably 20% by mass or less, and more preferably 5 to 15% by mass. The concentration can be arbitrarily selected among the concentration ranges, whereby the colloid formation can be suppressed to obtain a solution of -17-201107375. [Polyoxane solution] In the present invention, the polymerization solution obtained by the above method can be directly made into a solution of polyoxyalkylene, or the solution obtained by the above method can be concentrated and added to the solvent as necessary. Dilute' or replace with other solvents to make a solution of polyoxyalkylene. In this case, the solvent (hereinafter also referred to as "addition solvent") used may be the same as the polymerization solvent, and other solvents may be used. The solvent to be added is not particularly limited as long as it can uniformly dissolve the polyoxyalkylene, and can be used arbitrarily or in combination. Specific examples of the solvent to be added include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and methyl acetate, ethyl acetate, and lactic acid, in addition to the solvent exemplified as the above-mentioned polymerization solvent. Ester such as ethyl ester. These solvents can adjust the viscosity of the liquid crystal alignment agent or improve the coating property when the liquid crystal alignment agent is applied onto the substrate by spin coating, offset printing, ink jet or the like. [Other components] Among the liquid crystal alignment agents of the present invention, other components other than polysiloxane, such as inorganic fine particles, metal oxides (Metalloxane) oligomers, and metals, may be contained as long as the effects of the present invention are not impaired. Oxygen polymers, homogenizers, and even surfactants. The inorganic fine particles are preferably in the form of a colloidal solution, such as cerium oxide microparticles, alumina micro-18-201107375 particles, titanium dioxide microparticles, or magnesium fluoride microparticles. The colloidal solution is dispersed in a dispersion medium or may be commercially available. In the present invention, by containing inorganic fine particles, a surface shape and other functions can be imparted to the film. It is preferable that the inorganic fine particles have an average particle diameter of 0.001 to 2.2 μm, more preferably a hardened film formed by a coating liquid having an average particle diameter of inorganic fine particles exceeding 0.2 μm, and there is transparency in dispersion of inorganic fine particles. For the media, it can be listed. The colloidal solution is preferably adjusted to have a pH or a pKa of from 1 to 10 from the viewpoint of the coating liquid for film formation. Organic dissolved methanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, ethylene glycol monoethyl ethyl ketone, methyl group used in the dispersion medium of the colloidal solution Ketones such as isobutyl ketone; toluene, hydrocarbons; dimethylformamide, dimethylacetamide, N-decylamine; ethyl acetate, butyl acetate, r-butanfuran, I, 4 - ethers such as dioxane. Among these, it is better. These organic solvents may be used singly or in combination of two or more. A single precursor of a metal oxyalkylene oligomer, a metal oxyalkylene polymer, titanium, aluminum, molybdenum, niobium, tantalum, tin, indium, zinc, or the like. The metal oxyalkylene oligomer, the metal oxyalkylene polymer or the fine particles such as a metal alkoxide, a nitrate or a hydrochloric acid are preferred, and a colloidal solution of the inorganic fine particles is used. The formed hardened particles are in the range of 0.001 to Ο. ίμιη ,, and the use of the property is lowered. The viewpoint of the stability of water and the organic solvent is preferably 2 to 7. Examples of the agent include alcohols such as diol, pentanediol, and propyl ether; esters such as an ester such as aromatic methylpyrrolidone such as methylidene; and tetrahydrogen in the form of an alcohol or a ketone; In the case of the mono- or composite oxide compound, it can be obtained by a conventional method such as hydrolysis, such as a monohydrate or a carboxylate. For the specific examples of the metal oxide oligomer and the metal oxide polymer which are commercially available, "Methylsilicate 51 manufactured by Colcoat Co., Ltd."
Methylsilicate 53A、Ethylsilicate 40、Ethylsilicate 48、 EMS-485、SS-101等砂氧院寡聚物或砂氧院聚合物、關東 化學公司製之正丁氧基鈦四聚物等鈦氧烷（titanoxane ) 寡聚物。該等單獨或混合兩種以上使用皆可。 另外’均勻劑以及界面活性劑等，可使用周知者，特 別是市售品取得容易，故爲適合。 另外，於聚矽氧烷混合上述其他成分之方法，與聚矽 氧烷同時進行或者在之後進行皆可，並未特別受到限定。 [液晶配向劑] 本發明之液晶配向劑，係使上述聚矽氧烷溶解於溶劑 中，因應必要以溶解或分散的方式含有其他成分。就溶劑 而言’可使用選自上述聚矽氧烷之聚合溶劑及添加溶劑所 構成之群中之溶劑。液晶配向劑中之聚矽氧烷含量，以 Si〇2換算濃度表示宜爲0.5〜15質量％，較佳爲1〜6質量％ 。只要在如此的Si02換算濃度之範圍，以一次的塗佈即容 易得到所希望之膜厚，而且溶液之可使用時間容易變得充 足。 調製本發明之液晶配向劑之方法並未特別受到限定。 本發明所使用之聚矽氧烷，只要能使因應必要所加入的其 他成分均勻混合的狀態即可。通常是使聚矽氧烷在溶劑中 -20- 201107375 聚縮合’因此以直接使用聚矽氧烷之溶液，或者因應必要 在聚矽氧烷之溶液添加其他成分爲簡便。甚至，直接使用 聚矽氧烷之聚合溶液之方法最爲簡便。 另外，在調整液晶配向劑中之聚矽氧烷含量時，可使 用選自上述聚矽氧烷之聚合溶劑以及添加溶劑所構成之群 中之溶劑。 [液晶配向膜] 本發明之液晶配向膜，係使用上述液晶配向劑所得到 。例如，可將本發明之液晶配向劑塗佈於基板之後，進行 乾燥、燒成，將所得到之硬化膜直接作爲液晶配向膜使用 。另外，還可對該硬化膜實施刷磨（Rubbing )、或照射 偏光或特定波長之光線等、或實施離子束等處理，或者可 作爲PSA用配向膜，對於充塡液晶後的液晶顯示元件在施 加電壓的狀態照射U V。尤其有利於使用作爲p s A用配向膜 〇 就塗佈液晶配向劑之基板而言，只要是透明性高的基 板，則並未特別受到限定，而以在基板上形成液晶驅動用 的透明電極之基板爲佳。 若具體舉例，則可列舉在玻璃板、聚碳酸酯、聚（甲 基）丙烯酸酯、聚醚颯、聚芳香酯、聚胺甲酸乙酯、聚颯 、聚醚、聚醚酮、三甲基戊烯、聚烯烴、聚對苯二甲酸乙 二酯、（甲基）丙烯腈、三乙醯基纖維素、二乙醯基纖維 素、醋酸丁酸纖維素等塑膠板等形成透明電極之基板。 -21 - 201107375 就液晶配向劑之塗佈方法而言，可列舉旋轉塗佈法、 印刷法、噴墨法、噴霧法、輕式塗佈法等，而從生產性的 層面看來’工業上廣泛使用的轉印法，在本發明亦適合使 用。 塗佈液晶配向劑之後的乾燥步驟，未必是必須的，而 在每個基板塗佈後至燒成的時間並不固定的情況，或在塗 佈後並未立刻進行燒成的情況，係以包含乾燥步驟爲佳。 此乾燥’只要使溶劑除去至塗膜形狀不會因爲基板之搬運 等而變形的程度即可，對於此乾燥手段而言，並未特別受 到限定。可列舉例如在溫度4 0 °C〜1 5 0 °C (宜爲6 0 °C〜1 0 0 °C)之熱板上使其乾燥0.5〜30分鐘（宜爲1〜5分鐘）的 方法。 以上述方法塗佈液晶配向劑所形成的塗膜，可燒成而 製成硬化膜。此時，燒成溫度可在1 0 0 °C〜3 5 0 °c之任意溫 度進行，而宜爲140°C〜300 °C，較佳爲150°C〜230 °C、更 佳爲160°C〜220°C。燒成時間，以5分鐘〜240分鐘之任意 時間進行燒成皆可。宜爲10〜90分鐘，較佳爲20〜90分鐘 。加熱通常爲周知的方法，可使用例如熱板、熱風循環烘 箱、IR烘箱、帶式爐等。 液晶配向膜中之聚矽氧烷，係在燒成步驟之中進行聚 縮合。但是，在本發明中，只要不損及本發明之效果，沒 有必要使其完全聚縮合。但是，燒成溫度以高於在液晶胞 製造過程爲必要的封止劑硬化等熱處理的溫度1 ot以上爲 佳。 -22- 201107375 該硬化膜之厚度可因應必要而選擇，而宜爲5nm以上 ’較佳爲1 〇nm以上’此情況下可容易得到液晶顯示元件之 信賴性，故爲適合。另外，硬化膜之厚度宜爲300nm以下 ，較佳爲1 5 Onm以下’此情況下，液晶顯示元件之消耗電 力不會變得極大，故爲適合。 <液晶顯示元件> 本發明之液晶顯示元件，藉由上述方法，於基板形成 液晶配向膜之後，能夠以周知的方法製作而得到液晶胞。 若舉液晶胞製作之一例，則一般而言，以形成有液晶配向 膜的一對基板夾住間隔物，以封止劑固定，並且注入液晶 而密封的方法。此時所使用之間隔物大小爲1〜30μηι ,而 宜爲2〜ΙΟμιη。 注入液晶的方法並未特別受到限制，可列舉使所製作 的液晶胞內減壓之後注入液晶之真空法、滴入液晶之後進 行密封之滴入法等。 在PSΑ式液晶顯示元件中所使用之液晶，係使用添加 了少量光聚合性化合物（典型爲0.2〜1重量％ )之液晶。 藉由在導入此液晶之液晶胞之兩側基板電極間施加電壓的 狀態實施UV照射，聚合性化合物在當場發生聚合而交聯 ’而使得液晶顯示器之反應速度變快。此處所施加之電壓 爲5〜3〇Vp-p，而宜爲5〜20Vp-p。照射之UV照射量爲1〜 6〇J，而宜爲40J以下，UV照射量少者可抑制構成液晶顯示 器之構件的破壞所造成的信賴性降低，且減少UV照射時 -23- 201107375 間而使製造上效率提升，故爲適合。 就液晶顯示元件所使用之基板而言，只要是透明性高 之基板，則並未特別受到限定，而通常爲在基板上形成有 液晶驅動用透明電極之基板。具體例係與[液晶配向膜]所 記載之基板相同。可使用於P s A式液晶胞之基板，亦可採 用標準的PVA或Μ V A這樣的電極圖案或突起圖案。但是， 對於PS A式液晶顯示器而言，即使是於單側基板形成1〜 ΙΟμηι線寬/狹縫（line/slit )之電極圖案，於對向基板並未 形成狹縫圖案或突起圖案之構造亦可運作，藉由該構造之 液晶顯示器，可簡化製造時的程序，而能夠得到高透過率 〇 另外，在如TFT型元件般的高機能元件中，可採用在 液晶驅動用電極與基板之間形成電晶體這樣的元件。 在透過型之液晶顯示元件之情況，一般而言是使用如 上述的基板，而在反射型之液晶顯示元件中，若爲僅有單 側的基板，則亦可使用矽晶圓等不透明基板。此時，形成 於基板的電極亦可採用像鋁這樣會反射光線的材料》 [實施例] 以下藉由本發明之實施例進一步具體說明，而並未受 到該等限定而解釋。 在本實施例所使用的化合物中，略語如以下所述。 TEOS :四乙氧基矽烷 C18:十八烷基三乙氧基矽烷 24 201107375 ACPS: 丙烯醯氧基丙基三甲氧基砂院 HG : 2-甲基-2,4-戊二醇（別名：己二醇） BCS : 2-丁氧基乙醇 UPS : 3-脲丙基三乙氧基矽烷 MPMS : 3-甲基丙烯醯氧基丙基三甲氧基矽院 <實施合成例1 > 在設置有溫度計、回流管的200mL (毫升）四口 燒瓶中，混合 HG 22.5g、BCS 7.5g、TEOS 28.3g、 1.7g、以及ACPS 14.1g，調製出烷氧矽烷單體之溶液 室溫下，於此溶液花費30分鐘滴入預先混合了 HG 1 1. BCS 3.7g、水l〇.8g，以及作爲觸媒的草酸〇,2g之溶液 此溶液攪拌3 0分鐘之後，使其回流1小時然後放涼， 以Si02換算濃度表示爲12重量％之聚矽氧烷溶液。 於所得到之聚矽氧烷溶液1 0.0 g混合B C S 2 0.0 g， 以8丨02換算濃度表示爲4重量％之液晶配向劑（K1 )。 <實施合成例2 > 在設置有溫度計、回流管的200mL四口反應燒瓶 混合 HG 21.lg、BCS 7.0g、TEOS 19.2g、C1 8 1.7g、 ACPS 23.4g，調製出烷氧矽烷單體之溶液。在室溫下 此溶液花費30分鐘滴入預先混合了1^10.58、8〇3 3· 水10.8 g以及作爲觸媒的草酸0.9 g之溶液。 將此溶液攪拌30分鐘之後，使其回流1小時’然 反應 C 1 8 。在 2g、 。將 得到 得到 中， 以及 ，於 5g、 後加 -25- 201107375 入預先混合了 UPS含量92質量％之甲醇溶液1.2g、HG 0.5g ，以及BCS 0.2g的混合液。進一步使其回流30分鐘然後放 涼，得到以Si02換算濃度表示爲12重量％之聚矽氧烷溶液 〇 於所得到之聚矽氧烷溶液lO.Og混合BCS 20.0g，得到 以3102換算濃度表示爲4重量％之液晶配向劑（K2)。 <實施合成例3 > 在設置有溫度計、回流管的2 OOmL四口反應燒瓶中， 混合 HG 20.2g、BCS 6.7g、TEOS 27.9g、C1 8 1.7g、以及 MPMS 17.4g，調製出烷氧矽烷單體之溶液。在室溫下，於 此溶液花費30分鐘滴入預先混合了 HG lO.Og、BCS 3.4g、 水10.8g以及作爲觸媒的草酸〇.9g之溶液。 將此溶液攪拌3 0分鐘之後，使其回流1小時，然後加 入預先混合了 UPS含量92質量％之甲醇溶液〇.6g、HG 0.3g 以及BCS 0.1 g的混合液。進一步使其回流30分鐘然後放涼 ，得到以3丨02換算濃度表示爲12重量％之聚矽氧烷溶液。 於所得到之聚矽氧烷溶液10.0g混合BCS 20.0g，得到 以3102換算濃度表示爲4重量％之液晶配向劑（K3 )。 <比較合成例1 > 在設置有溫度計、回流管的200mL四口反應燒瓶中， 混合 HG 23.3g、BCS 7.7g、TEOS 40.8g、C18 1.7g，調製 出烷氧矽烷單體之溶液。在室溫下，於此溶液花費3 0分鐘 -26- 201107375 滴入預先混合了 HG 11.6g、BCS 3.9g、水l〇.8g以及作爲觸 媒的草酸0.2g之溶液。 將此溶液攪拌3 0分鐘之後，使其回流1小時然後放涼 ，得到Si02換算固體成分濃度爲12重量％之聚矽氧烷溶液 〇 於所得到之聚矽氧烷溶液10.0g混合BCS 20.0g’得到 以3丨02換算濃度表示爲4重量％之液晶配向劑（L1)。 <實施例1 > 將合成例1所得到之液晶配向處理劑[K1 ]旋轉塗佈於 形成有畫素尺寸爲1〇〇μπΐχ300μπι，而且線寬/間距（ line/space)分別爲5μιη之ΙΤΟ電極圖案之ΙΤΟ電極基板之 ΙΤΟ面。在80°c之熱板乾燥5分鐘之後，在18CTC之熱風循 環式烘箱進行燒成30分鐘，形成膜厚lOOnm之液晶配向膜 〇 將合成例1所得到之液晶配向處理劑[K1 ]旋轉塗佈於 並未形成電極圖案之ITO面，在80°c之熱板乾燥5分鐘之後 ，在180 °C之熱風循環式烘箱進行燒成30分鐘，形成膜厚 lOOnm之液晶配向膜。準備該等兩片基板，在其中一個基 板之液晶配向膜面上塗佈6μπι之珠狀間隔物（bead spacer )之後，由其上方印刷封止劑。以液晶配向膜面爲內側， 將另一個基板貼合之後，使封止劑硬化而製作出空槽。製 作出液晶對於MLC-6608 ( Merck公司製商品名）添加了式 (S -1 )所表示之聚合性化合物0.2重量。/。之液晶，對空槽 -27- 201107375 實施減壓注入法，藉此製作注入有前述液晶之液晶胞。 [化1]Aluminium oxide (titanoxane) such as Methylsilicate 53A, Ethylsilicate 40, Ethylsilicate 48, EMS-485, SS-101, etc., or a sand oxide compound or a non-butoxy titanium tetramer made by Kanto Chemical Co., Ltd. Oligomer. These may be used alone or in combination of two or more. Further, it is suitable to use a known agent, a surfactant, and the like, and it is easy to use a known product, particularly a commercially available product. Further, the method of mixing the above-mentioned other components with polyoxymethane may be carried out simultaneously with or after the polysiloxane, and is not particularly limited. [Liquid crystal alignment agent] The liquid crystal alignment agent of the present invention dissolves the above polysiloxane in a solvent, and if necessary, contains other components in a dissolved or dispersed manner. As the solvent, a solvent selected from the group consisting of a polymerization solvent of the above polyoxyalkylene and a solvent may be used. The polysiloxane content in the liquid crystal alignment agent is preferably from 0.5 to 15% by mass, preferably from 1 to 6% by mass, based on the Si〇2 conversion concentration. As long as such a concentration in the range of SiO 2 is applied, the desired film thickness can be easily obtained by one application, and the usable time of the solution is likely to be sufficient. The method of preparing the liquid crystal alignment agent of the present invention is not particularly limited. The polyoxyalkylene used in the present invention may be in a state of being uniformly mixed with other components to be added as necessary. It is usually a polycondensation of polyoxyalkylene in a solvent -20- 201107375. Therefore, it is convenient to use a solution of polyoxyalkylene directly, or to add other components in a solution of polyoxyalkylene as necessary. Even the method of directly using a polymerization solution of polyoxyalkylene is the easiest. Further, when adjusting the content of the polyoxyalkylene in the liquid crystal alignment agent, a solvent selected from the group consisting of the above-mentioned polymerization solvent of polyoxyalkylene and a solvent may be used. [Liquid Crystal Alignment Film] The liquid crystal alignment film of the present invention is obtained by using the above liquid crystal alignment agent. For example, the liquid crystal alignment agent of the present invention can be applied to a substrate, dried, and fired, and the obtained cured film can be directly used as a liquid crystal alignment film. Further, the cured film may be subjected to rubbing, irradiation of polarized light or light of a specific wavelength, or treatment such as ion beam, or may be used as an alignment film for PSA, and the liquid crystal display element after charging the liquid crystal is The state in which the voltage is applied is irradiated with UV. In particular, it is advantageous to use a substrate in which a liquid crystal alignment agent is applied as an alignment film for ps A, and is not particularly limited as long as it is a substrate having high transparency, and a transparent electrode for driving a liquid crystal is formed on the substrate. The substrate is preferred. Specific examples include glass plates, polycarbonates, poly(meth)acrylates, polyether oximes, polyaromatic esters, polyurethanes, polyfluorenes, polyethers, polyether ketones, and trimethyl groups. a substrate for forming a transparent electrode such as a pentene, a polyolefin, a polyethylene terephthalate, a (meth)acrylonitrile, a triethylenesulfonyl cellulose, a diethyl cellulose, a cellulose acetate butyrate or the like . -21 - 201107375 The coating method of the liquid crystal alignment agent includes a spin coating method, a printing method, an inkjet method, a spray method, a light coating method, and the like, and it is industrially A widely used transfer method is also suitable for use in the present invention. The drying step after the application of the liquid crystal alignment agent is not necessarily required, and the case where the baking time is not fixed after the application of each substrate or the case where the baking is not performed immediately after the coating is performed. It is preferred to include a drying step. This drying is not particularly limited as long as the solvent is removed until the shape of the coating film is not deformed by the conveyance of the substrate or the like. The drying means is not particularly limited. For example, a method of drying at a temperature of 40 ° C to 150 ° C (preferably 60 ° C to 1 0 0 ° C) for 0.5 to 30 minutes (preferably 1 to 5 minutes) is exemplified. . The coating film formed by coating the liquid crystal alignment agent by the above method can be fired to form a cured film. In this case, the firing temperature may be carried out at any temperature of from 100 ° C to 3 50 ° C, and is preferably from 140 ° C to 300 ° C, preferably from 150 ° C to 230 ° C, more preferably 160. °C ~ 220 °C. The firing time can be carried out at any time from 5 minutes to 240 minutes. It should be 10 to 90 minutes, preferably 20 to 90 minutes. The heating is usually a well-known method, and for example, a hot plate, a hot air circulating oven, an IR oven, a belt furnace, or the like can be used. The polyoxyalkylene in the liquid crystal alignment film is subjected to polycondensation in the firing step. However, in the present invention, it is not necessary to completely condense the condensation as long as the effects of the present invention are not impaired. However, the firing temperature is preferably at least 1 ton higher than the temperature of the heat treatment such as hardening of the sealant which is necessary for the production process of the liquid crystal cell. -22-201107375 The thickness of the cured film can be selected as necessary, and is preferably 5 nm or more, preferably 1 〇 nm or more. In this case, the reliability of the liquid crystal display element can be easily obtained, which is suitable. Further, the thickness of the cured film is preferably 300 nm or less, preferably 15 nm or less. In this case, the power consumption of the liquid crystal display element does not become extremely large, which is suitable. <Liquid Crystal Display Element> The liquid crystal display element of the present invention can be produced by a known method to form a liquid crystal cell after forming a liquid crystal alignment film on a substrate by the above method. In the case of the liquid crystal cell production, in general, a spacer is sandwiched between a pair of substrates on which a liquid crystal alignment film is formed, and a sealing agent is fixed, and a liquid crystal is injected and sealed. The spacer used at this time has a size of 1 to 30 μm, and preferably 2 to ΙΟμιη. The method of injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which a liquid crystal is produced by depressurizing the liquid crystal, and a dropping method in which a liquid crystal is dropped and then sealed. The liquid crystal used in the PS-type liquid crystal display device is a liquid crystal to which a small amount of a photopolymerizable compound (typically 0.2 to 1% by weight) is added. By applying UV irradiation in a state where a voltage is applied between the substrate electrodes on both sides of the liquid crystal cell into which the liquid crystal is introduced, the polymerizable compound is polymerized on the spot to be crosslinked, and the reaction speed of the liquid crystal display is increased. The voltage applied here is 5 to 3 〇 Vp-p, and preferably 5 to 20 Vp-p. The UV irradiation amount of the irradiation is 1 to 6 〇J, and preferably 40 J or less, and the amount of UV irradiation is small, the reliability of the damage of the member constituting the liquid crystal display can be suppressed, and the UV irradiation can be reduced between -23 and 201107375. It is suitable for improving the efficiency of manufacturing. The substrate used for the liquid crystal display device is not particularly limited as long as it is a substrate having high transparency, and is usually a substrate on which a transparent electrode for driving a liquid crystal is formed on a substrate. The specific example is the same as the substrate described in [Liquid Crystal Alignment Film]. The substrate for the P s A type liquid crystal cell can be used, or an electrode pattern or a protrusion pattern such as a standard PVA or Μ V A can be used. However, in the case of the PS A type liquid crystal display, even if the electrode pattern of 1 to ΙΟμηι line width/slit is formed on the single-sided substrate, the slit pattern or the protrusion pattern is not formed on the opposite substrate. It is also possible to operate the liquid crystal display of the structure, and it is possible to simplify the process at the time of manufacture, and to obtain a high transmittance. In addition, in a high-performance element such as a TFT type element, an electrode for liquid crystal driving and a substrate can be used. An element such as a transistor is formed. In the case of a transmissive liquid crystal display device, generally, a substrate as described above is used. In the case of a reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as long as it has only a single substrate. At this time, the electrode formed on the substrate may also be a material that reflects light such as aluminum. [Embodiment] Hereinafter, it will be further specifically explained by the embodiment of the present invention, and is not explained by the limitation. In the compounds used in the examples, the abbreviations are as described below. TEOS: Tetraethoxydecane C18: Octadecyltriethoxydecane 24 201107375 ACPS: Propylene methoxypropyltrimethoxy sand court HG: 2-methyl-2,4-pentanediol (alias: Hexanediol) BCS: 2-butoxyethanol UPS: 3-ureidopropyltriethoxydecane MPMS: 3-methylpropenyloxypropyltrimethoxysulfonate <Example of Synthesis Example 1 > A 200 mL (ml) four-necked flask equipped with a thermometer and a reflux tube was mixed with HG 22.5 g, BCS 7.5 g, TEOS 28.3 g, 1.7 g, and ACPS 14.1 g to prepare a solution of alkoxysilane monomer at room temperature. This solution was dropped into HG 1 1. BCS 3.7 g, water l〇.8 g, and oxalic acid oxalate as a catalyst, and 2 g of this solution was stirred for 30 minutes, and then refluxed for 1 hour. It was allowed to cool, and the concentration of Si02 was 12% by weight of a polyoxyalkylene solution. 1 0.0 g of the obtained polyoxane solution was mixed with B C S 2 0.0 g, and the concentration of the liquid crystal alignment agent (K1) was 4% by weight in terms of a concentration of 8 丨 02. <Preparation of Synthesis Example 2 > In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, HG 21.lg, BCS 7.0 g, TEOS 19.2 g, C1 8 1.7 g, and ACPS 23.4 g were mixed to prepare an alkoxydecane single. Body solution. This solution was dropped into a solution of 1 g of 10.58, 8 〇 3 3 · water 10.8 g and 0.9 g of oxalic acid as a catalyst at room temperature for 30 minutes. After the solution was stirred for 30 minutes, it was refluxed for 1 hour to react C 1 8 . In 2g, . A mixture of 1.2 g of a methanol solution having a UPS content of 92% by mass, 0.5 g of HG, and 0.2 g of BCS previously mixed with 5 g and then -25 to 201107375 was added. Further, the mixture was refluxed for 30 minutes and then allowed to cool to obtain a polyoxynitane solution having a concentration of 12% by weight in terms of SiO 2 , and a solution of 20.0 g of a BCS obtained by mixing the obtained polyoxyxane solution 100.0 g to obtain a concentration of 3102. It is a 4% by weight liquid crystal alignment agent (K2). <Preparation of Synthesis Example 3 > In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 20.2 g of HG, 6.7 g of BCS, 27.9 g of TEOS, 1.7 g of C1 8 and 17.4 g of MPMS were mixed to prepare an alkane. A solution of oxoxane monomer. At room temperature, a solution of HG10.Og, BCS 3.4 g, water 10.8 g, and cerium oxalate as a catalyst was added dropwise to the solution for 30 minutes. After the solution was stirred for 30 minutes, it was refluxed for 1 hour, and then a mixed solution of a methanol solution of 92.6 g, HG 0.3 g and BCS 0.1 g previously mixed with a UPS content of 92% by mass was added. Further, the mixture was refluxed for 30 minutes and then allowed to cool to obtain a polyoxysilane solution having a concentration of 3 丨 02 in terms of 12% by weight. 20.0 g of BCS was mixed with 10.0 g of the obtained polyoxane solution to obtain a liquid crystal alignment agent (K3) represented by a concentration of 3102 in an amount of 4% by weight. <Comparative Synthesis Example 1 > In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 23.3 g of HG, 7.7 g of BCS, 40.8 g of TEOS, and 1.7 g of C18 were mixed to prepare a solution of an alkoxysilane monomer. At room temperature, this solution took 30 minutes. -26-201107375 A solution of HG 11.6 g, BCS 3.9 g, water l.8 g and 0.2 g of oxalic acid as a catalyst was added dropwise. After the solution was stirred for 30 minutes, it was refluxed for 1 hour and then allowed to cool to obtain a polyoxane solution having a solid concentration of 12% by weight in terms of SiO 2 , and 10.0 g of the obtained polyoxane solution was mixed with BCS 20.0 g. 'A liquid crystal alignment agent (L1) represented by a concentration of 3丨02 as 4% by weight was obtained. <Example 1> The liquid crystal alignment treatment agent [K1] obtained in Synthesis Example 1 was spin-coated on a pixel having a size of 1 〇〇μπΐχ300 μm, and the line/space was 5 μm. The top surface of the electrode substrate of the tantalum electrode pattern. After drying on a hot plate at 80 ° C for 5 minutes, it was baked in a hot air circulating oven of 18 CTC for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. The liquid crystal alignment treatment agent [K1 ] obtained in Synthesis Example 1 was spin-coated. The ITO surface which was not formed with the electrode pattern was dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating oven at 180 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. These two substrates were prepared, and a 6 μm bead spacer was applied to the liquid crystal alignment film surface of one of the substrates, and then a sealant was printed thereon. After the liquid crystal alignment film surface is inside, after bonding the other substrate, the sealing agent is cured to form an empty groove. In the liquid crystal, 0.2 weight of the polymerizable compound represented by the formula (S-1) was added to MLC-6608 (trade name, manufactured by Merck Co., Ltd.). /. Liquid crystal, vacant groove -27- 201107375 A vacuum injection method is applied to produce a liquid crystal cell into which the liquid crystal is injected. [Chemical 1]
藉由後述方法測定該等液晶胞之反應速度特性。其後 ，在對該液晶胞施加20Vp-p電壓的狀態，由此液晶胞外側 照射UV 20J。其後，再次測定反應速度特性，並與UV照 射前後之反應速度（單位ms :毫秒）作比較。將其結果揭 示於表1。 <實施例2 > 除了將添加於液晶MLC-6608之聚合性化合物變更爲 0.05重量％以外，係以與實施例1相同的方式測定反應速度 。將結果揭示於表1。 <實施例3 > 除了將添加於液晶MLC-6608之聚合性化合物變更爲 0.0 2重量％以外，係以與實施例1相同的方式測定反應速度 。將結果揭示於表1。 <實施例4 > 除了不添加聚合性化合物於液晶MLC-6608以外，係 -28 - 201107375 以與實施例1相同的方式測定反應速度。將結果揭 <實施例5 > 除了將液晶配向處理劑[K1 ]變更爲實施合成{ 到之液晶配向處理劑[Κ2]以外，係以與實施例4相 式製作液晶胞’測定反應速度。將其結果揭示於表 <實施例6 > 除了將液晶配向處理劑[Κ1]變更爲實施合成召 到之液晶配向處理劑[Κ3]以外，係以與實施例4相 式製作液晶胞，測定反應速度。將其結果揭示於表 <比較例1〜比較例4 > 除了將液晶配向處理劑[Κ1 ]變更爲比較合成召 到之液晶配向處理劑[L 1 ]以外，係以與實施例1〜1 相同的方式，製作液晶胞，測定反應速度。將其結 於表1。 [反應速度特性] 對並未施加電壓之液晶胞施加電壓± 4 V、頻率 矩形波時，以示波器截取液晶面板輝度隨時間的變 未施加電壓時之輝度爲0 %，以± 4 V之施加電壓、飽 度値爲1 〇 〇 %，將輝度由1 0 %變成9 0 %的時間定爲暗 於表1 U 2所得 同的方 Ϊ 3所得 同的方 J 1所得 f施例4 果揭示 1kHz 之 化。以 和之輝 轉亮（ -29 - 201107375The reaction rate characteristics of the liquid crystal cells were measured by the method described later. Thereafter, a state of 20 Vp-p voltage was applied to the liquid crystal cell, whereby UV 20J was irradiated to the outside of the liquid crystal cell. Thereafter, the reaction rate characteristics were measured again and compared with the reaction speed (unit: ms: milliseconds) before and after the UV irradiation. The results are shown in Table 1. <Example 2> The reaction rate was measured in the same manner as in Example 1 except that the polymerizable compound added to the liquid crystal MLC-6608 was changed to 0.05% by weight. The results are disclosed in Table 1. <Example 3> The reaction rate was measured in the same manner as in Example 1 except that the polymerizable compound added to the liquid crystal MLC-6608 was changed to 0.02% by weight. The results are disclosed in Table 1. <Example 4> The reaction rate was measured in the same manner as in Example 1 except that the polymerizable compound was not added to the liquid crystal MLC-6608, -28 - 201107375. The results are as follows. Example 5 > In addition to changing the liquid crystal alignment treatment agent [K1] to the synthesis of the liquid crystal alignment treatment agent [Κ2], the reaction rate was measured by preparing the liquid crystal cell with the phase of the fourth embodiment. . The results are disclosed in the table <Example 6 > In addition to changing the liquid crystal alignment treatment agent [Κ1] to the liquid crystal alignment treatment agent [Κ3] for performing the synthesis, the liquid crystal cell was produced in the same manner as in Example 4, The reaction rate was measured. The results are shown in Table <Comparative Example 1 to Comparative Example 4 > In addition to changing the liquid crystal alignment treatment agent [Κ1] to the liquid crystal alignment treatment agent [L1] which is comparatively synthesized, it is the same as Example 1 1 In the same manner, a liquid crystal cell was produced and the reaction rate was measured. Let it be listed in Table 1. [Reaction Velocity Characteristics] When a voltage of ± 4 V or a rectangular wave is applied to a liquid crystal cell to which no voltage is applied, the luminance of the liquid crystal panel is changed with time by an oscilloscope, and the luminance is 0%, and the application is applied at ± 4 V. The voltage and saturation 値 are 1 〇〇%, and the time when the luminance is changed from 10% to 90% is determined to be darker than that obtained in Table 1 U 2 . The same square J 1 is obtained. Example 4 reveals 1kHz. Reconcile with He Hui ( -29 - 201107375
Rising)之反應速度。 [表1] 液晶配向劑 聚合性化合物之添加量 反應速度转 F性（ms) (質量％) UV照射前 uv照射後 實施例1 K1 0.2 800 < <50 實施例2 K1 0.05 800< <50 實施例3 K1 0.02 800 < 230 實施例4 K1 — 800< 240 實施例5 K2 — 800 < <50 實施例6 K3 — 800 < <50 比較例1 L1 0.2 800 < <50 比較例2 L1 0.05 800 < 170 比較例3 L1 0.02 800 < 800 < 比較例4 L1 — 800 < 800 < 由表1可知，實施例之液晶胞，即使在聚合性化合物 減爲0.05重量％的情況，UV照射後之反應速度也會提升至 與聚合性化合物0.2重量％時相同的程度。再者，即使在聚 合性化合物定爲0.02重量％的情況，反應速度也會提升。 甚至在使用未添加聚合性化合物之液晶的情況，反應速度 也會提升。在實施例5、6中，係以未添加聚合性化合物之 液晶實施，而反應速度大幅提升。另一方面，在比較例中 ，減少或未添加聚合性化合物之液晶的情況下，反應速度 並未提升。 產業上之可利用性 使用本發明之液晶配向劑所製作之液晶顯示元件，在 -30- 201107375 PS A式的配向方式之中，即使在減少聚合性化合物的情況 ，仍然可提升反應速度，能夠得到良好的配向狀態，甚至 在使用未添加聚合性化合物之液晶的情況，也能夠提供可 得到與PSA式同等特性之液晶顯示元件。此結果顯示，在 P S A式T F T液晶顯示元件、T N液晶顯示元件、v A液晶顯示 元件等方面是有用的。 另外’將在2009年5月1日所申請之日本專利申請第 2009-112197號以及在2009年10月29日所申請之日本專利 申請第2009-2493 〇1號之說明書、申請專利範圍、以及發 明摘要之全部內容引用於此，收錄爲本發明說明書之揭示 -31 -Rising) reaction rate. [Table 1] Addition amount of liquid crystal alignment agent polymerizable compound Reaction rate to F (ms) (% by mass) Example 1 after UV irradiation, after uv irradiation K1 0.2800 <50 Example 2 K1 0.05 800 << 50 Example 3 K1 0.02 800 < 230 Example 4 K1 - 800 < 240 Example 5 K2 - 800 < 50 Example 6 K3 - 800 < 50 Comparative Example 1 L1 0.2 800 << 50 Comparative Example 2 L1 0.05 800 < 170 Comparative Example 3 L1 0.02 800 < 800 < Comparative Example 4 L1 - 800 < 800 < As can be seen from Table 1, the liquid crystal cell of the example was reduced even in the polymerizable compound In the case of 0.05% by weight, the reaction rate after UV irradiation was also increased to the same extent as in the case of 0.2% by weight of the polymerizable compound. Further, even in the case where the polymerizable compound was set to 0.02% by weight, the reaction rate was increased. Even in the case of using a liquid crystal to which no polymerizable compound is added, the reaction speed is increased. In Examples 5 and 6, the liquid crystal was not added with a polymerizable compound, and the reaction rate was greatly improved. On the other hand, in the comparative example, when the liquid crystal of the polymerizable compound was reduced or not added, the reaction rate did not increase. Industrial Applicability The liquid crystal display element produced by using the liquid crystal alignment agent of the present invention can increase the reaction rate even in the case of reducing the polymerizable compound among the alignment modes of the -30-201107375 PS A type. A good alignment state is obtained, and even when a liquid crystal to which a polymerizable compound is not added is used, a liquid crystal display element which can obtain the same characteristics as the PSA type can be provided. This result shows that it is useful in a P S A type T F T liquid crystal display element, a T N liquid crystal display element, a v A liquid crystal display element, and the like. In addition, the specification of the Japanese Patent Application No. 2009-112197, filed on May 1, 2009, and the Japanese Patent Application No. 2009-2493 〇1, filed on Oct. 29, 2009, The entire disclosure of the Abstract is hereby incorporated by reference in its entirety in its entirety