201245334 六、發明說明 【發明所屬之技術領域】 由本發明關於一種液晶配向劑，其係含有使烷氧矽烷 聚縮合所得到的聚矽氧烷；一種液晶配向膜，其係由前述 液晶配向劑所得到；以及一種液晶顯示元件，其係具有該 液晶配向膜。 【先前技術】 近年來，在液晶顯示元件的顯示方式之中，垂直（VA) 型液晶顯示元件被廣泛利用在大畫面液晶電視或高精細行 動電話用途（數位相機或行動電話的顯示部位）等。 關於 VA 型，已知有 MVA 型（Multi Vertical Alignment)，其係在TFT板或彩色濾光基板中形成用以控 制液晶倒下的方向的突起；或PVA(Patterned Vertioal Alignment)型，其係在基板的ITO電極形成狹縫，藉由電 場控制液晶倒下的方向。 其他配向方式還有 PSA(Polymer sustained Alignment) 型。在VA型之中，PSA型是近年受到矚目的技術。此方 式是在液晶中添加光聚合性化合物而製作出液晶面板後， 施加電場使液晶倒下，在此狀態下對液晶面板照射UV。 其結果’藉由聚合性化合物進行光聚合反應使液晶的配向 方向固定化’會發生預傾（pre-tilt)，而反應速度提升。在 構成液晶面板的單側電極製作出狹縫，其特徵爲即使是對 向側的電極圖型並未設置如MVA般的突起或如PVA般的 201245334 狹縫的構造亦可運作，製造過程簡化或可得到優異的面板 透過率。（參照專利文獻1) 已知的液晶配向膜材料除了以往所使用的聚醯亞胺等 的有機系液晶配向膜材料之外，還有無機系液晶配向膜材 料。例如有文獻提出一種配向劑組成物，其係含有四烷氧 矽烷、三烷氧矽烷、醇類及草酸的反應生成物以作爲塗佈 型無機系配向膜之材料，並且報告了一種液晶配向膜，其 係在液晶顯示元件的電極基板上形成垂直配向性、耐熱性 及均勻性優異。（參照專利文獻2) 另外還有文獻提出一種液晶配向劑組成物，其係含有 與四烷氧矽烷，特定的三烷氧矽烷及水的反應生成物與特 定的甘醇醚系溶劑，並且報告了形成一種液晶配向膜，防 止顯示不良，長時間驅動後殘像特性亦爲良好的，不會使 液晶配向的能力降低，且對於光及熱的電壓保持率的降低 幅度小。（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2004-302061號公報 專利文獻2:日本特開平09-281502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] 在P S A型液晶顯示元件之中，添加於液晶中的聚合 201245334 性化合物的溶解性低，若增加添加量則會有在低溫時析出 的問題。另一方面，若減少聚合性化合物的添加量，則無 法得到良好的配向狀態。另外，液晶中所殘留未反應的聚 合性化合物，會成爲液晶中的雜質（污染物），因此會有降 低液晶顯示元件信賴性這樣的問題。對於這個問題，藉由 在配向膜中導入可進行聚合反應的側鏈，則即使是使用未 添加聚合性化合物的液晶的情況，仍可得到與PSA型同 等的特性。 在垂直配向的VA型之中，爲了產生垂直配向必須有 強的垂直配向力，然而這種方式並未使用聚合性化合物， 若提升垂直配向力，則UV照射後的反應速度變慢，若提 升UV照射後的反應速度，則垂直配向力降低。垂直配向 力與UV照射後的反應速度的提升互爲抵換（trade-off)的 關係。 本發明之課題在於提供一種液晶配向劑，其係使用不 添加聚合性化合物之液晶，與PSA型同樣地進行處理， 可形成一種液晶配向膜，即使是在提升UV照射後的反應 速度的液晶顯示元件之中，也不會降低垂直配向力，並且 可提升UV照射後的反應速度；以及一種液晶顯示元件， 其係具有由該液晶配向劑所得到的液晶配向膜。 [用於解決課題之手段] 本發明的要旨如下。 [1 ] 一種液晶配向劑，其係含有下述聚矽氧烷（A)及 201245334 聚矽氧烷（B): 聚矽氧烷（A):使含有式（1)所表示之烷氧矽烷及式（2)所表 示之烷氧矽烷的烷氧矽烷聚縮合所得到的聚矽氧烷： FMS i (OR2) 3 (1 ) (R1爲可經氟原子取代且碳數8〜30之烴基，R2表示碳數 1〜5之烷基） R3S i (0R4) 3 (2) (R3爲經丙烯醯基、甲基丙烯醯基或芳香基取代之碳數1 〜30之烷基，R4表示碳數1〜5之烷基） 聚砂氧烷（B):使含有式（3)所表示之烷氧矽烷70 %〜100% 的烷氧矽烷聚縮合所得到的聚矽氧烷： s ' (OR5) 4 (3) (R5表示碳數1〜5之烷基p [2] 如上述[1 ]所記載之液晶配向劑，其中聚矽氧烷 (B Μ系進一步使含有式（2)所表示之烷氧矽烷的烷氧矽烷聚 縮合所得到的聚矽氧烷。 [3] 如上述[1]所記載之液晶配向劑，其中聚矽氧烷 (ΒΗ系進一步使含有式（4)所表示之烷氧矽烷的烷氧矽烷聚 縮合所得到的聚矽氧烷： R6S i (0R7) 3 (4) (r6爲碳數1〜5之烷基，r7表示碳數i〜5之烷基）。 [4] 如上述Π]〜[3]之任一項所記載之液晶配向劑， 其中選自聚矽氧烷（A)及聚矽氧烷（B)之至少一種之聚矽氧 201245334 烷係進一步使含有下述式（5)所表示之烷氧矽烷的烷氧矽 烷聚縮合所得到的聚矽氧烷。 (R8) nS i (OR9) 4-n (5) (R8爲氫原子、或可經雜原子、鹵素原子、胺基、縮水甘 油醚基、锍基、異氰酸酯基或脲基取代且碳數1〜12之烴 基，R9爲碳數1〜5之烷基’ η爲表示〇〜3之整數）。 [5] 如上述Π]〜[3]之任一項所記載之液晶配向劑， 其中在聚矽氧烷（Α)所使用的烷氧矽烷全體之中，含有前 述式（1)所表示之烷氧矽烷1莫耳％〜20莫耳％，且在聚矽 氧烷（Α)所使用的烷氧矽烷全體之中，含有前述式（2)所表 示之烷氧矽烷10莫耳％〜80莫耳％。 [6] —種液晶配向膜，其係將如上述[1]〜[5]之任一 項所記載之液晶配向劑塗佈於基板，使其乾燥並且燒成所 得到。 [7] —種液晶顯示元件，其係具有如上述[6]所記載 之液晶配向膜。 [8] —種液晶顯示元件，其係對於以塗佈如上述[1] 〜[5]之任一項所記載之液晶配向劑且經過燒成的兩枚基 板夾住液晶的液晶槽，在施加電壓的狀態下照射UV所得 到。 [9] 一種液晶顯示元件之製造方法，其係以塗佈如上 述[1 ]〜[5 ]之任一項所記載之液晶配向劑且經過燒成的兩 枚基板夾住液晶，並在施加電壓的狀態下照射UV。 201245334 [發明之效果] 依據本發明，藉由使用不添加聚合性化合物之液晶， 並與PSA型同樣地照射UV，可得到一種液晶配向劑，其 係可形成不會使垂直配向力降低，並可提升UV照射後的 反應速度的液晶配向膜；以及一種液晶顯示元件，其係具 有由該液晶配向劑所得到的液晶配向膜。 【實施方式】 〈聚砂氧院（A) > 聚矽氧烷（A)係使含有式（1)所表示之烷氧矽烷及式（2) 所表示之烷氧矽烷的烷氧矽烷聚縮合所得到的聚矽氧烷。 R'S i (OR2) 3 (1 ) 式（1)中，R1爲可經氟原子取代且碳數8〜30之烴基，R2 表示碳數1〜5之烷基。 R3S i (0R4) 3 (2) 式（2)中，R3爲經丙烯醯基、甲基丙烯醯基或芳香基取代 之烷基，R4表示碳數1〜5之烷基。 式（1)所表示之烷氧矽烷之R1(以下亦稱爲特定有機基） 係可經氟取代之碳數爲8〜30(宜爲8〜22)之烴基，只要 是具有使液晶垂直配向的效果的物質，則不受特別限定。 特定有機基的例子可列舉烷基、氟烷基、烯基、苯乙 基基、苯乙烯基烷基、萘基、氟苯基烷基等。該等之中， 以R1爲烷基、或氟烷基的烷氧矽烷容易以較低價的市售 品的形式取得，故爲適合。上述氟烷基之中，氟原子數爲 -10- 201245334 1以上，全部的氫皆可經氟原子取代。 尤其以R1爲烷基的烷氧矽烷爲佳。本發明所使用的 聚矽氧烷（A)亦可具有多種這些特定的有機基。 式（1)所表示之烷氧矽烷之R2的碳數1〜5,宜爲1〜 3之烷基。較佳爲R2爲甲基或乙蕋。 以下列舉這種由式（1)所表示之烷氧矽烷的具體例 子，然而並不受其限定。 可列舉例如辛基三甲氧基矽烷、辛基三乙氧基矽烷、 癸基三甲氧基矽烷、癸基三乙氧基矽烷、十二烷基三甲氧 基矽烷、十二烷基三乙氧基矽烷、十六烷基三甲氧基矽 烷、十六烷基三乙氧基矽烷、十七烷基三甲氧基矽烷、十 七烷基三乙氧基矽烷、十八烷基三甲氧基矽烷、十八烷基 三乙氧基矽烷、十九烷基三甲氧基矽烷、十九烷基三乙氧 基矽烷、十一烷基三乙氧基矽烷、十一烷基三甲氧基矽 烷、21-二十二烯基三乙氧基矽烷、十三氟辛基三甲氧基 矽烷、十三氟辛基三乙氧基矽烷、十七氟癸基三甲氧基矽 烷、十七氟癸基三乙氧基矽烷、異辛基三乙氧基矽烷、苯 乙基三乙氧基矽烷、五氟苯基丙基三甲氧基矽烷、間苯乙 烯基乙基三甲氧基矽烷、對苯乙烯基乙基三甲氧基矽烷、 (1-萘基）三乙氧基矽烷、（卜萘基）三甲氧基矽烷等。其中 以辛基三甲氧基矽烷、辛基三乙氧基矽烷、癸基三甲氧基 矽烷、癸基三乙氧基矽烷、十二烷基三甲氧基矽烷、十二 烷基三乙氧基矽烷、十六烷基三甲氧基矽烷、十六烷基三 乙氧基矽烷、十七烷基三甲氧基矽烷、十七烷基三乙氧基 -11 - 201245334 矽烷、十八烷基三甲氧基矽烷、十八烷基三乙氧基矽烷、 十九烷基三甲氧基矽烷、十九烷基三乙氧基矽烷、十一烷 基三乙氧基矽烷、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，具有上述特定有機基之 式U)所表示之烷氧矽烷，係以在爲了得到聚矽氧烷（A)所 使用的全部的烷氧矽烷之中佔1莫耳％以上爲佳。較佳爲 1.5莫耳％以上。更佳爲2莫耳％以上。另外，爲了使所形 成的液晶配向膜得到充分的硬化特性，以3 0莫耳％以下 爲佳。較佳爲2 5莫耳％以下。 式（2)所表示之烷氧矽烷之R3(以下亦稱爲第二特定有 機基）爲經選自丙烯醯基、甲基丙烯醯基及芳香基所構成 之群中之至少一者取代之烷基。經取代的氫原子爲一個以 上’宜爲一個。烷基的碳數係以1〜30爲佳，較佳爲1〜 2〇°更佳爲1〜10。烷基可爲直鏈狀或分支狀，而以直鏈 狀爲較佳。 式（2)所表示之烷氧矽烷之R4爲碳數1〜5之烷基， 宜爲碳數1〜3，特佳爲碳數1〜2。 以下列舉式（2)所表示之烷氧矽烷的具體例子，然而 並不受該等所限定。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、苯乙烯基乙基三甲氧基矽烷、苯 -12- 201245334 乙烯基乙基三乙氧基矽烷、3-(Ν·苯乙燃基甲基-2·胺乙基 胺基）丙基三甲氧基矽烷。 在聚矽氧烷（A)之製造中’除了式（1)及式（2)所表示之 院氧砂垸以外，爲了改善與基板的密著性、與液晶分子的 親和性等目的，在不損及本發明效果的前提下’亦可使用 一種或多種下述式（5)所表示之烷氧矽烷。式（5)所表示之 烷氧矽烷可對聚矽氧烷賦予各種特性’因此可因應必要特 性選擇一種或多種來使用。 (R8) nS i (OR9) 4_n (5) 式（5)中，R8爲氫原子、或可經雜原子、鹵素原子、 胺基、縮水甘油醚基、毓基、異氰酸酯基或脲基取代且碳 數1〜1 〇之烴基。 R9爲碳數1〜5(宜爲1〜3)之烷基。 η爲0〜3(宜爲〇〜2)之整數。 式（5)所表示之烷氧矽烷之R8爲氫原子或碳數爲1〜 10之烴基（以下亦稱爲第三特定有機基）。 第三特定有機基的例子，例如脂肪族烴基；脂肪族 環、芳香族環及雜環般的環構造之烴基；具有不飽和鍵的 烴基；可含有氧原子、氮原子、硫原子等的雜原子等，亦 可具有分支構造，碳數爲1〜6之烴基。第三特定有機基 亦可經齒素原子、胺基、縮水甘油醚基、巯基、異氰酸酯 基、脲基等取代。 以下列舉式（5)所表示之烷氧矽烷之具體例，然而並 不受其限定。可列舉3_(2_胺乙基胺丙基）三甲氧基矽烷、 -13- 201245334 3-(2-胺乙基胺丙基）三乙氧基矽烷、2-胺乙基胺基甲基三 甲氧基矽烷' 2-(2-胺乙基硫代乙基）三乙氧基矽烷、3-毓 丙基三乙氧基矽烷、巯基甲基三甲氧基矽烷、乙烯基三乙 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、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、3 _胺丙 基甲基二乙氧基矽烷、3-胺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、r-脲丙基三乙氧基 矽烷、r-脲丙基三甲氧基矽烷及r-脲丙基三丙氧基矽烷 等。 式（5)所表示之烷氧矽烷之中n爲0的烷氧矽烷係四 烷氧矽烷。四烷氧矽烷容易與式（1)〜（4)所表示之烷氧矽 烷縮合’因此可得到本發明之聚矽氧烷（Α)，故爲適合。 這種式（5)之中η爲〇的烷氧矽烷，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，尤其以四甲氧基矽烷或四乙氧基矽烷爲佳。 在本發明中，在聚矽氧烷（Α)之製造所使用的全部的 烷氧矽烷中’宜爲含有式（1)所表示之烷氧矽烷1莫耳％〜 20莫耳％，特佳爲2莫耳％〜20莫耳％，且在聚矽氧烷（Α) 之製造所使用的全部的烷氧矽烷中，宜爲含有式（2)所表 示之烷氧矽烷10莫耳％〜80莫耳％，特佳爲30莫耳％〜 8 0莫耳％。 -14 - 201245334 〈聚砂氧院（B) > 聚矽氧烷（B)係使含有式（3)所表示之烷氧矽烷70重 量％〜1 00重量％的烷氧矽烷聚縮合所得到的聚矽氧烷。 S i (〇R5) 4 (3) 式（3)中，R5表示碳數1〜5之烷基，宜爲碳數1或2。 這種式（3)所表示之烷氧矽烷的具體例子，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’尤其以四甲氧基矽烷或四乙氧基矽烷爲佳。 聚矽氧烷（B)除了式（3)所表示之烷氧矽烷以外，進一 步還可爲使含有式（2)所表示之烷氧矽烷之烷氧矽烷聚縮 合所得到的聚矽氧烷。 聚矽氧烷（B)所含的式（2)所表示之烷氧矽烷可採用在 上述聚矽氧烷（A)之製造之中所使用的烷氧矽烷。關於其 具體例子亦與上述同樣。 聚矽氧烷（B)除了式（3)所表示之烷氧矽烷以外，進一 步還可爲使含有式（4)所表示之烷氧矽烷的烷氧矽烷聚縮 合所得到的聚矽氧烷。 R6S i (OR，）3 (4) 式（4)中，R6爲碳數1〜5之烷基，R7表示碳數1〜5之烷 基》 式（4)所表示之烷氧矽烷之R6爲碳數1〜5之烷基。烷基 之碳數係以1〜4爲佳，較佳爲1〜3。 式（4)所表示之烷氧矽烷之R7爲碳數1〜5之烷基，宜爲 -15- 201245334 碳數1〜3，特佳爲碳數1〜2。 以下列舉式（4)所表示之烷氧矽烷的具體例子，然而 並不受該等所限定。例如甲基三乙氧基矽烷、甲基三甲氧 基矽烷、二甲基三甲氧基矽烷、二甲基三乙氧基矽烷、正 丙基三甲氧基矽烷、正丙基三乙氧基矽烷。 特別是這種液晶配向劑，除了含有式（3)所表示之烷 氧矽烷以外，還進一步含有聚矽氧烷（B)，該聚矽氧烷（B) 係使含有式（4)所表示之烷氧矽烷的烷氧矽烷聚縮合所得 到，其垂直配向力高，而爲特別合適。 爲了藉由使用未添加聚合性化合物的液晶，施加電壓 同時進行UV照射以提升液晶顯示元件的反應速度，具有 第二特定有機基的由式（2)所表示之烷氧矽烷，係以在爲 了得到聚矽氧烷（B)所使用的全部的烷氧矽烷中佔1〇莫耳 %以上爲佳。較佳爲20莫耳％以上。更佳爲30莫耳％以 上。另外，爲了使所形成的液晶配向膜充分硬化，係以 75莫耳％以下爲佳。 在製造聚矽氧烷（B)時，除了由式（2)、式（3)及式（4) 所表示之烷氧矽烷以外，以改善基板的密著性、與液晶分 子的親和性等爲目的’在不損及本發明效果的前提下，亦 可使用一種或多種下述式（5)所表示之烷氧矽烷。式（5)所 表示之烷氧矽烷可對聚矽氧烷賦予各種特性，因此可因應 必要特性選擇一種或多種來使用。 (R8) nS i (OR9) 4_n (5) 式（5)中，R8及R9的構造及合適的範圍、式（5)所表示之 -16- 201245334 烷氧矽烷之具體例如先前所述。 <聚矽氧烷之製造方法〉 用以得到本發明所使用的聚矽氧烷之方法並未受到特 別限定。本發明之聚矽氧烷（A)係使以上述式（1)及式（2)爲 必須成分的烷氧矽烷在有機溶劑中聚縮合所得到；而聚矽 氧烷（B)係使以上述式（3)爲必須成分的烷氧矽烷在有機溶 劑中聚縮合所得到。通常聚矽氧烷是使這樣的烷氧矽烷聚 縮合，並均勻溶解於有機溶劑而製成溶液所得到。 使烷氧矽烷聚縮合之方法，可列舉例如使烷氧矽烷在 醇類或甘醇類等的溶劑中水解、縮合之方法。此時，水 解、縮合反應可爲部分水解及完全水解之任一者。在完全 水解的情況下，理論上只要加入烷氧矽烷中的全部的烷氧 基之0.5倍莫耳的水即可，而通常宜加入過量0.5倍莫耳 的水。 在本發明中，上述反應所使用的水量可依照希望適當 地選擇，而通常以烷氧矽烷中之全部的烷氧基之0.5倍莫 耳〜2.5倍莫耳爲佳，1倍莫耳〜2倍莫耳爲較佳。 另外，通常爲了促進水解、縮合反應，可使用鹽酸、 硫酸、硝酸、醋酸、犠酸、草酸、馬來酸、富馬酸等的 酸；氨、甲胺、乙胺、乙醇胺、三乙胺等的鹼；鹽酸、硫 酸、硝酸等的金屬鹽等的觸媒。此外，一般而言還可藉由 將溶有烷氧矽烷的溶液加熱，進一步促進水解、縮合反 應。此時，加熱溫度及加熱時間可依照希望適當地選擇。 -17- 201245334 可列舉例如在5 0 °C下加熱、攪拌2 4小時、在回流下加 熱、攪拌1小時等的方法》 另外，其他方法可列舉例如將烷氧矽烷、溶劑及草酸 之混合物加熱而使其聚縮合之方法。具體而言，如預先在 醇中加入草酸而製成草酸的醇溶液，然後在加熱的狀態 下，將該溶液與烷氧矽烷混合之方法。此時，所使用的草 酸量係以定爲相對於烷氧矽烷所具有的全部的烷氧基之1 莫耳而言的〇_2莫耳〜2莫耳爲佳，以0.5莫耳〜1.5莫耳 爲較佳。此方法中的加熱可在液溫50 °C〜180 °C進行》宜 爲不會發生液體蒸發、揮發等現象的方式，在回流下加熱 數十分鐘〜十數小時之方法。 在得到聚矽氧烷時使用多種烷氧矽烷的情況可預先將 烷氧矽烷混合而製成混合物使用，或可依序混合多種烷氧 矽烷來使用。 使烷氧矽烷聚縮合時所使用的溶劑（以下亦稱爲聚合 溶劑）只要可使烷氧矽烷溶解，則不受特別限定。另外， 在烷氧矽烷不溶解的情況，只要是可使烷氧矽烷進行聚縮 合反應同時溶解的物質即可。一般而言藉由烷氧矽烷之聚 縮合反應而產生醇，因此可使用醇類、甘醇類、甘醇醚 類、或醇類相溶性的良好的有機溶劑，尤其適合使用甘醇 類。 這樣的聚合溶劑之具體例可列舉甲醇、乙醇、丙醇、 丁醇、二丙酮醇等的醇類；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 -18- 201245334 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-己二醇等的甘醇類；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、丙二醇二丁醚等的甘醇醚類；N -甲基-2-吡咯 烷酮、N，N -二甲基甲醯胺、Ν,Ν -二甲基乙醯胺、r-丁內 酯、二甲亞楓、四甲基尿素、六甲基磷酸三醯胺、間甲酚 等。在本發明中，亦可將多種上述聚合溶劑混合使用。 上述方法所得到的聚矽氧烷之聚合溶液（以下亦稱爲 聚合溶液）’以將作爲原料所裝入的全部的烷氧矽烷之矽 原子換算成Si〇2所得的濃度（以下稱爲Si〇2換算濃度）而 計’宜爲2 0重量％以下’進一步以定爲5重量％〜丨5重 量％爲較佳。藉由在此濃度範圍選擇任意濃度，可抑制膠 體的產生而得到均質的溶液。 <聚矽氧烷之溶液> 在本發明中，可將上述方法所得到的聚合溶、液直接製 成聚矽氧烷之溶液。另外還可因應必要將上述方法所得到 的溶液濃縮或加入溶劑稀釋，或置換成其他溶齊彳，製成聚 -19- 201245334 矽氧烷之溶液。 此時所使用的溶劑（以下亦稱爲添加溶劑）可與聚合溶 劑相同，或可爲其他溶劑。在聚矽氧烷均勻溶解的前提 下，此添加溶劑並未受到特別限定，可任意地選擇一種或 多種來使用。 這種添加溶劑之具體例，除了上述聚合溶劑的例子所 列舉的溶劑之外，還可列舉丙酮、甲基乙基酮、甲基異丁 基酮等的酮類；醋酸甲酯、醋酸乙酯、乳酸乙酯等的酯 類。 這些溶劑可調整液晶配向劑之黏度、或可提升在藉由 旋轉塗佈、膠版印刷、噴墨等將液晶配向劑塗佈於基板上 時的塗佈性。 <其他成分> 在本發明中，在不損及本發明效果的前提下，在聚矽 氧烷之溶液中亦可含有聚矽氧烷以外的其他成分，例如無 機微粒子、金屬氧烷寡聚物、金屬氧烷聚合物、均勻劑、 進一步界面活性劑等的成分。 無機微粒子係以二氧化矽微粒子、氧化鋁微粒子、二 氧化鈦微粒子、氟化鎂微粒子等的微粒子爲佳，尤其以膠 體溶液的狀態爲佳。此膠體溶液可爲使無機微粒子分散於 分散媒而成的溶液，或可爲市售品的膠體溶液。在本發明 中，藉由含有無機微粒子，可對所形成的硬化被膜賦予表 面形狀以及其他機能。無機微粒子其平均粒徑係以 -20- 201245334 Ο.ΟΟΙμιη〜0.2μιη爲佳，更佳爲Ο.ΟΟΙμηι〜Ο.ίμηι。在無機 微粒子的平均粒徑超過0.2 μιη的情況下，使用調製出的塗 佈液所形成的硬化被膜，會有透明性降低的情形。 無機微粒子的分散媒可列舉水及有機溶劑。從被膜形 成用塗佈液之安定性的觀點看來，膠體溶液的ΡΗ或pKa 係以調整成1〜1 〇爲佳。較佳爲2〜7。 膠體溶液之分散媒所使用的有機溶劑可列舉甲醇、丙 醇、丁醇、乙二醇、丙二醇、丁二醇、戊二醇、己二醇、 二乙二醇、二丙二醇、乙二醇單丙醚等的醇類；甲基乙基 酮、甲基異丁基酮等的酮類；甲苯、二甲苯等的芳香族烴 類；二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮等的 醯胺類；醋酸乙酯、醋酸丁酯、r-丁內酯等的酯類：四 氫呋喃、1,4 -二噁烷等的醚類》該等之中係以醇類或酮類 爲佳》這些有機溶劑可單獨或混合2種以上使用作爲分散 媒。 金屬氧烷寡聚物及金屬氧烷聚合物可使用矽、鈦、 鋁、钽、銻、鉍、錫、銦、鋅等的單獨或複合氧化物前驅 物。由金屬氧烷寡聚物及金屬氧烷聚合物可爲市售品、或 可爲金屬烷氧化物、硝酸鹽、鹽酸鹽、羧酸鹽等的單體， 藉由水解等的常法所得到的物質。 市售品之金屬氧烷寡聚物及金屬氧烷聚合物的具體例 子可列舉 Colcoat 公司製的、Methylsilicate 51 、 Methylsilicate 5 3 A、E t h y 1 s i 1 i c a t e s 40、 Ethyl silicates 48、EMS_485、SS-101等的矽氧烷寡聚物或矽氧院聚合 -21 - 201245334 物、關東化學公司製的正丁氧基鈦四聚物等的鈦氧烷寡聚 物。該等可單獨或混合2種以上來使用。 另外，均勻劑及界面活性劑等可使用周知的物質，尤 其是市售品容易取得，故爲適合。 另外，在聚矽氧烷中混合上述其他成分的方法，可與 聚矽氧烷同時或在之後進行，並未受到特別限定。 [液晶配向劑] 本發明之液晶配向劑，係含有上述聚矽氧烷，因應必 要含有其他成分的溶液。此時，溶劑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。 在液晶配向劑中的全聚矽氧烷的含量以Si02換算濃 度而計，宜爲〇. 5重量％〜1 5重量％、較佳爲1重量％〜6 重量％。只要在這樣的Si 02換算濃度的範圍，即能夠容易 以一次塗佈得到所希望之膜厚，並且容易得到足夠的溶液 使用期（pot life)。 本發明之液晶配向劑係含有聚矽氧烷（A)與聚矽氧烷 (B)，在全部的聚矽氧烷中以重量比而計爲1〇 : 90〜50 : 50 > 宜爲 20 : 80 〜40 : 60。 另外，在本發明之液晶配向劑中的全聚矽氧烷與因應 必要添加的其他成分的重量比爲99: 1〜50: 50，宜爲 98 : 2〜70 : 30 。 調製本發明之液晶配向劑之方法並未受到特別限定。 本發明所使用的聚矽氧烷，只要使因應必要添加的其他成 -22- 201245334 分呈均勻混合的狀態即可。通常聚矽氧烷是在溶 合，因此簡便的方法是直接使用聚矽氧烷的溶液 矽氧烷的溶液中因應必要添加其他成分。進一步 直接使用聚矽氧烷的聚合溶液的方法最爲簡便。 另外，在調整液晶配向劑中的聚矽氧烷的含 使用選自上述烷氧矽烷之聚合溶劑及聚矽氧烷之 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本發明之液晶 得。例如可將本發明之液晶配向劑塗佈於基板， 乾燥、燒成，將所得到的硬化膜直接作爲液晶 用。另外，此硬化膜還可經過摩擦、照射偏光或 的光線等、或進行離子束等的處理、或在對液晶 液晶顯示元件施加電壓的狀態下照射UV。 塗佈液晶配向劑的基板只要是透明性的高的 受特別限定，而以在基板上形成有用以驅動液晶 極之基板爲佳。 若列舉具體例子，則可列舉在玻璃板、聚碳 (甲基）丙烯酸酯、聚醚颯、聚芳酯、聚胺甲酸 颯、聚醚、聚醚酮、三甲基戊烯、聚烯烴、聚對 乙二酯、（甲基）丙烯腈、三乙醯纖維素、二乙 素、醋酸丁酸纖維素等的塑膠板等形成透明電極 液晶配向劑之塗佈方法，可列舉旋轉塗佈 劑中聚縮 ，或在聚 而言，以 量時，可 添加溶劑 配向劑而 然後進行 配向膜使 特定波長 塡充後的 基板則不 的透明電 酸酯、聚 乙酯、聚 苯二甲酸 醯基纖維 的基板。 法、印刷 -23- 201245334 法、噴墨法、噴霧法、輕式塗佈法等，而從生產力的層面 看來，工業上廣泛使用的轉印法亦適合使用於本發明。 在塗佈液晶配向劑之後未必需要乾燥步驟，而在塗佈 後至燒成爲止的時間隨著各個基板而改變的情況，或塗佈 後並未立刻燒成的情況，係以包含乾燥步驟爲佳。此乾燥 只要在不會因爲基板的搬運等而發生塗膜形狀變形的程 度，並可將溶劑除去即可，關於其乾燥手段並未受到特別 限定。可列舉例如在溫度4 0 °C〜1 5 0 °c (宜爲6 0 °c〜1 00 °c ) 之熱板上乾燥〇·5分鐘〜30分鐘（宜爲1分鐘〜5分鐘）之 方法。 以上述方法塗佈液晶配向劑所形成的塗膜，可進行燒 成而製成硬化膜。此時，燒成溫度可在100°C〜35(TC的 任意溫度進行，而宜爲140°C〜3 00 °C ^較佳爲150°C〜 23 0 °C、更佳爲160°C〜220°C。燒成時間能夠以5分鐘〜 240分鐘的任意時間進行燒成。宜爲10分鐘〜90分鐘， 較佳爲20分鐘〜80分鐘。加熱通常可使用周知的方法， 例如熱板、熱風循環烘箱、IR(紅外線）烘箱、帶式爐等。 液晶配向膜中的聚矽氧烷會在燒成步驟中進行聚縮 合。但是，在本發明中，在不損及本發明效果的前提下， 並沒有必要完全使其聚縮合》但是以在高於液晶槽製造步 驟所須的密封劑硬化等的熱處理溫度1 〇 t以上的溫度燒 成爲佳。 此硬化膜的厚度可因應必要來選擇，而宜爲5nm以 上，較佳爲l〇nm以上，由於可容易得到液晶顯示元件的 -24- 201245334 信賴性，因此爲適合的。另外，硬化膜的厚度宜爲3 OOnrr 以下，較佳爲150nm以下，由於液晶顯示元件的消費電 力不會變得極大，因此爲適合的。 <液晶顯示元件> 本發明之液晶顯示元件，可藉由上述方法，在基板形 成液晶配向膜之後，藉由周知的方法製作出液晶槽而得。 若列舉液晶槽製作的一例，則一般而言有以形成有液 晶配向膜的一對基板將間隔件包夾住，並以密封劑固定， 注入液晶並且密封的方法。此時，所使用的間隔件大小爲 Ιμιη〜30μηι，而宜爲 2μηι 〜ΙΟμιη。 注入液晶的方法並未受到特別限制，可列舉使所製作 的液晶槽內減壓之後注入液晶的真空法、在滴入液晶之後 進行密封的滴入法等。 藉由對於導入了液晶的液晶槽之兩側基板的電極間， 在施加電壓的狀態下UV照射，配向膜中的丙烯醯基、甲 基丙烯醯基等會在此處聚合而交聯，液晶顯示器的反應速 度變快。此處’施加的電壓爲5Vp-p〜50Vp-p，而宜爲 5Vp-p〜30Vp-p。所照射的UV照射量爲1 J(焦耳）〜60J， 而宜爲40J以下。UV照射量少的情況可抑制信賴性（構成 液晶顯示器的構件不會破壞的特性）降低，且減少U V照 射時間’生產節拍（工作量）提高，故爲適合。 液晶顯示元件中使用的基板只要是透明性的高的基 板’則並未受到特別限定’而通常爲在基板上形成有用以 -25- 201245334 驅動液晶的透明電極之基板。具體例係與[液晶配向膜]所 記載的基板同樣。亦可使用標準的所謂PVA或MVA這種 具有電極圖型或突起圖型的基板。 關於液晶顯示元件所使用的基板，與PSA型液晶顯 示器同樣地，在單側基板形成1 μπι〜1 Ομηι的線寬/狹縫電 極圖型，在對向基板並未形成狹縫圖型或突起圖型的構造 之中亦可運作，藉由此構造的液晶顯示器，可簡化製造時 的程序，能夠得到高透過率。 另外，在如TFT型液晶顯示元件般的高機能液晶顯 示元件之中，亦可採用在用以驅動液晶的電極與基板之 間，在基板上形成有電晶體元件者。 在透射型液晶顯示元件的情況，一般是使用如上述般 的基板，而在反射型液晶顯示元件中，可採用僅在單側基 板反射光線的鋁這樣的材料，亦可採用矽晶圓等的不透明 基板。 [實施例] 以下藉由實施例，對本發明作進一步具體說明，然而 本發明並不受該等限定地解釋。 本實施例所使用的化合物的略語如以下所述。 TEOS :四乙氧基矽烷 C18:十八烷基三乙氧基矽烷 ACPS: 3-丙烯醯氧基丙基三甲氧基矽烷 MPMS: 3-甲基丙烯醯氧基丙基三甲氧基矽烷 -26- 201245334 MTES :甲基三乙氧基矽烷 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 <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 20.6g 的 HG、6.9g 的 BCS、18.3g 的 TEOS、 4.2g的C18及23.4g的ACPS，而調製出烷氧矽烷單體之 溶液。在此溶液中，在室溫下花費30分鐘滴入預先將 10.3g的HG、3.4g的BCS、l〇.8g的水、及作爲觸媒的 l.4g的草酸.混合而得的溶液，進一步在室溫下攪拌30分 鐘。然後使用油浴加熱，使其回流30分鐘之後，加入預 先將UPS含量92質量％的甲醇溶液〇.6g、0.3g的HG及 O.lg的BCS混合而得的混合液。進一步使其回流30分鐘 然後放涼，而得到Si02換算濃度爲12重量％之聚矽氧烷 溶液。 將所得到的聚矽氧烷溶液l〇.〇g與20.0g的BCS加以 混合，而得到Si02換算濃度爲4重量％之液晶配向劑中間 體（S1)。 另外，在設置有溫度計、回流管的200mL四口反應 燒瓶中，混合23.6g的HG、7_9g的BCS及41 .2g的 TEOS，而調製出烷氧矽烷單體之溶液。在此溶液中，在 室溫下花費30分鐘滴入預先將1 1.8g的HG、3.9g的 -27- 201245334 BCS、10.8g的水 '及0.2g作爲觸媒的草酸混合而得的溶 液，進一步在室溫下攪拌30分鐘。然後使用油浴加熱， 使其回流30分鐘之後，加入預先將UPS含量92質量％之 甲醇溶液〇.6g、0.3g的HG及O.lg的BCS混合而得的混 合液。進一步使其回流30分鐘然後放涼，而得到Si02換 算濃度爲1 2重量％之聚矽氧烷溶液。 將所得到的聚矽氧烷溶液l〇.〇g與2〇.〇g的BCS加以 混合，而得到s i 02換算濃度爲4重量％之液晶配向劑中間 體（U 1)»將所得到的液晶配向劑中間體（s 1)與液晶配向劑 中間體（u 1)以3 : 7的比率（重量比’以下相同）混合’而 得到Si02換算濃度爲4重量％之液晶配向劑[K1]。 <合成例2 > 在設置有溫度計、回流管的20 0mL四口反應燒瓶 中，混合 19.9g 的 HG、6.6g 的 BCS、18.3g 的 TEOS、 4.2g的C18及24.8g的MPMS，而調製出院氧砂焼單體之 溶液。在此溶液中，在室溫下花費30分鐘滴入預先將 lO.Og的HG、3.3g的BCS、10.8g的水、及1.4g作爲觸媒 的草酸混合而得的溶液’進—步在室溫下攪拌30分鐘。 然後，使用油浴加熱’使其回流30分鐘之後’加入預先 將UPS含量92質量％之甲醇溶液0.6g、〇.3g的HG及 O.lg的BCS混合而得的混合液。進一步使其回流30分鐘 然後放涼，而得到Si〇2換算濃度爲1 2重量％之聚砂氧烷 溶液。 -28- 201245334 將所得到的聚矽氧烷溶液1 0.0 g與2 0.0 g的B C S加以 混合，而得到Si02換算濃度爲4重量％之液晶配向劑中間 體（S2)。將所得到的液晶配向劑中間體（S2)與合成例1所 得到的液晶配向劑中間體（U 1)以3 : 7的比率混合，而得 到Si02換算濃度爲4重量％之液晶配向劑[K2]。 <合成例3 > 在設置有溫度計、回流管的200mL四口反應燒瓶 中，混合 23.3g 的 HG、7.8g 的 BCS、39.2g 的 TEOS 及 2.5g的MPMS，而調製出烷氧矽烷單體之溶液。在此溶液 中，在室溫下花費30分鐘滴入預先將11.7g的HG' 3.9g 的BCS、10.8g的水、及0.4g作爲觸媒的草酸混合而得的 溶液，進一步在室溫下攪拌30分鐘。然後，使用油浴加 熱使其回流30分鐘之後，加入預先將UPS含量92質量％ 之甲醇溶液〇.6g、0.3g的HG及O.lg的BCS混合而得的 混合液。進一步使其回流30分鐘然後放涼，而得到Si02 換算濃度爲12重量％之聚矽氧烷溶液。 將所得到的聚矽氧烷溶液l〇.〇g與20.0g的BCS加以 混合，而得到Si02換算濃度爲4重量％之液晶配向劑中間 體（U2)。將合成例1所得到的液晶配向劑中間體（S 1)所得 到的液晶配向劑中間體（U2)以3 : 7的比率混合，而得到 Si02換算濃度爲4重量％之液晶配向劑[K3] » <合成例4 > -29 - 201245334 將合成例2所得到的液晶配向劑中間體（S2)與合成例 3所得到的液晶配向劑中間體（U2)以3 : 7的比率混合， 而得到Si02換算濃度爲4重量％之液晶配向劑[K4]。 <合成例5 > 在設置有溫度計、回流管的 200mL四口反應燒瓶 中，混合 23.8g 的 NG、7.9g 的 BCS、37.1g 的 TEOS 及 3.6g的MTES，而調製出烷氧矽烷單體之溶液。在此溶液 中，在室溫下花費30分鐘滴入預先將11.9g的HG、4.0g 的BCS、10.8g的水、及0.4g作爲觸媒的草酸混合而得的 溶液，進一步在室溫下攪拌3 0分鐘。然後使用油浴加 熱，使其回流30分鐘之後，加入預先將UPS含量92質 量％之甲醇溶液〇.6g、0.3g的HG及O.lg的BCS混合而 得的混合液。進一步使其回流3 0分鐘然後放涼，而得到 Si〇2換算濃度爲12重量％之聚矽氧烷溶液。 將所得到的聚矽氧烷溶液l〇.〇g與20.0g的BCS加以 混合，而得到Si〇2換算濃度爲4重量％之液晶配向劑中間 體（U3) »將合成例1所得到的液晶配向劑中間體（S1)與所 得到的液晶配向劑中間體（U 3 )以3 : 7的比率混合，而得 到Si02換算濃度爲4重量％之液晶配向劑[K5]。 <合成例6 > 將合成例2所得到的液晶配向劑中間體（S2)_合成例 5所得到的液晶配向劑中間體（U3)以3 : 7的比率混合， -30- 201245334 而得到Si〇2換算濃度爲4重量％之液晶配向劑[Κ6] » <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 22.6g 的 HG、7.5g 的 BCS、39.6g 的 TEOS，而 調製出烷氧矽烷單體之溶液。在此溶液中，在室溫下花費 30分鐘滴入預先將11.3g的HG、3.8g的BCS、10.8g的 水、及0.2g作爲觸媒的草酸混合而得的溶液，進一步在 室溫下攪拌3 0分鐘。然後，使用油浴加熱，使其回流1 小時然後放涼，而得到Si02換算濃度爲12重量％之聚矽 氧烷溶液。將所得到的聚矽氧烷溶液10. 〇g與20.0g的 BCS加以混合，而得到Si02換算濃度爲4重量％之液晶配 向劑[L 1 ]。 <比較合成例2 > 以與合成例1所得到的液晶配向劑中間體（S 1)同樣的 方式得到液晶配向劑[L2]。 <比較合成例3 > 以與合成例2所得到的液晶配向劑中間體（S2)同樣的 方式得到液晶配向劑[L3]。 <實施例1 > 將合成例1所得到的液晶配向處理劑[K1 ]旋轉塗佈於 -31 - 201245334 ITO電極基板之ITO面，該基板形成有畫素大小爲100微 米X 3 00微米，線寬/間距分別爲5微米的ΙΤΟ電極圖型。 以80°C之熱板乾燥2分鐘之後，以200°C或220t之熱風 循環式烘箱進行燒成30分鐘，形成膜厚l〇〇nm的液晶配 向膜。將合成例1所得到的液晶配向處理劑[K1 ]旋轉塗佈 於並未形成電極圖型的ITO面，以80°C的熱板乾燥2分 鐘之後，與上述基板同樣地，以200°C或220°C的熱風循 環式烘箱進行燒成30分鐘，形成膜厚lOOnm的液晶配向 膜。準備這樣的兩枚基板，將6μηι的珠粒間隔物散布在 其中一個基板的液晶配向膜面上之後，將密封劑印刷於其 上。以液晶配向膜面爲內側將另一個基板貼合之後，使密 封劑硬化，而製作出空槽。將液晶MLC-6608(Merck公司 製商品名）藉由減壓注入法注入至空槽中，而製作出液晶 槽。 藉由後述方法，對於所得到的液晶槽的反應速度特性 進行測定。然後，在此液晶槽中20Vp-p之在施加電壓的 狀態下，由此液晶槽的外側照射UV(使用波長365nm的 帶通濾光片）2〇J。然後，再度測定反應速度特性，並比較 UV照射前後的反應速度。將其結果揭示於表！。 另外’關於槽的垂直配向性亦藉由後述方法測定以及 評估。將其結果一倂揭示於表1。 <實施例2 > 除了將液晶配向處理劑[K 1 ]變更爲合成例2所得到的 -32- 201245334 液晶配向處理劑[K2]以外，係以與實施例1同樣的方式製 作出液晶槽，並測定反應速度。將其結果揭示於表1。 <實施例3 > 除了將液晶配向處理劑[Κ1 ]變更爲合成例3所得到的 液晶配向處理劑[Κ3]以外，係以與實施例1同樣的方式製 作出液晶槽，並測定反應速度。將其結果揭示於表1。 <實施例4 > 除了將液晶配向處理劑[Κ1 ]變更爲合成例4所得到的 液晶配向處理劑[Κ4]以外，係以與實施例1同樣的方式製 作出液晶槽，並測定反應速度。將其結果揭示於表1。 <實施例5 > 除了將液晶配向處理劑[Κ1]變更爲合成例5所得到的 液晶配向處理劑[Κ5]以外，係以與實施例1同樣的方式製 作出液晶槽，並測定反應速度。將其結果揭示於表1 » <實施例6 > 除了將液晶配向處理劑[Κ1]變更爲合成例6所得到的 液晶配向處理劑[Κ6]以外，係以與實施例1同樣的方式製 作出液晶槽，並測定反應速度。將其結果揭示於表1。 <比較例1 > -33- 201245334 除了將液晶配向處理劑[κ 1 ]變更爲比較合成例1所得 到的液晶配向處理劑[L1 ]以外，係以與實施例1同樣的方 式製作出液晶槽，並測定反應速度。將其結果揭示於表 <比較例2 > 除了將液晶配向處理劑[Κ1]變更爲比較合成例2所得 到的液晶配向處理劑[L2]以外，係以與實施例1同樣的方 式製作出液晶槽，並測定反應速度。將其結果揭示於表 <比較例3〉 除了將液晶配向處理劑[Κ1]變更爲比較合成例2所得 到的液晶配向處理劑[L3 ]以外，係以與實施例1同樣的方 式製作出液晶槽，並測定反應速度。將其結果揭示於表 [反應速度特性] 在對並未施加電壓的液晶槽施加電壓±4V、頻率1kHz 的方波時，將液晶面板的輝度隨時間的變化記錄在示波 器。將並未施加電壓時的輝度定爲0%、施加±4V電壓時 飽和的輝度値定爲100%，將輝度由10%變化爲90%的時 間定爲上升反應速度。 -34- 201245334 [垂直配向性] 關於垂直配向性的評估，係在配置於正交偏光的兩枚 偏光板之間配置槽體並進行觀察，判定是否表現出黑顯 示°提高燒成溫度’將愈能夠表現出垂直配向性的情形評 爲垂直配向性愈高。 [表1]201245334 VI. Description of the Invention [Technical Field] The present invention relates to a liquid crystal alignment agent comprising a polyoxyalkylene obtained by polycondensation of an alkoxysilane; a liquid crystal alignment film which is provided by the liquid crystal alignment agent And a liquid crystal display element having the liquid crystal alignment film. [Prior Art] In recent years, vertical (VA) type liquid crystal display elements have been widely used in large-screen liquid crystal televisions or high-definition mobile phones (display positions of digital cameras or mobile phones) among display modes of liquid crystal display elements. . Regarding the VA type, a MVA type (Multi Vertical Alignment) is known which is formed in a TFT plate or a color filter substrate to form a protrusion for controlling the direction in which the liquid crystal falls down; or a PVA (Patterned Vertioal Alignment) type, which is attached to The ITO electrode of the substrate forms a slit, and the direction in which the liquid crystal falls down is controlled by an electric field. Other alignment methods are PSA (Polymer sustained Alignment) type. Among the VA types, the PSA type is a technology that has attracted attention in recent years. In this method, after a liquid crystal panel is added to a liquid crystal to produce a liquid crystal panel, an electric field is applied to cause the liquid crystal to fall, and in this state, the liquid crystal panel is irradiated with UV. As a result, the photopolymerization reaction of the polymerizable compound causes the alignment direction of the liquid crystal to be fixed, and pre-tilt occurs, and the reaction rate is increased. A slit is formed in the one-side electrode constituting the liquid crystal panel, and the electrode pattern of the opposite side is not provided with an MVA-like protrusion or a PVA-like 201245334 slit structure, and the manufacturing process is simplified. Or excellent panel transmittance can be obtained. (Patent Document 1) A known liquid crystal alignment film material includes an inorganic liquid crystal alignment film material such as polyimine which is conventionally used, and an inorganic liquid crystal alignment film material. For example, there has been proposed a composition of an alignment agent containing a reaction product of a tetraalkanooxane, a trialkoxide, an alcohol, and an oxalic acid as a material of a coating type inorganic alignment film, and a liquid crystal alignment film is reported. It is excellent in vertical alignment, heat resistance, and uniformity on the electrode substrate of the liquid crystal display element. (Refer to Patent Document 2) There is also a liquid crystal alignment agent composition which contains a reaction product with a tetraalkoxysilane, a specific trialkoxysilane and water and a specific glycol ether solvent, and reports thereon. A liquid crystal alignment film is formed to prevent display defects, and the afterimage characteristics are also good after long-time driving, the ability to align the liquid crystal is not lowered, and the voltage reduction ratio of light and heat is small. (Patent Document 3) Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problems to be Solved by the Invention] Among the PSA liquid crystal display devices, the solubility of the polymerized 201245334 compound added to the liquid crystal is low, and if the amount of addition is increased, there is a problem that precipitation occurs at a low temperature. On the other hand, if the amount of the polymerizable compound added is reduced, a good alignment state cannot be obtained. Further, since the unreacted polymer compound remaining in the liquid crystal becomes an impurity (contaminant) in the liquid crystal, there is a problem that the reliability of the liquid crystal display element is lowered. In this case, by introducing a side chain capable of undergoing a polymerization reaction into the alignment film, even when a liquid crystal to which a polymerizable compound is not added is used, the same characteristics as those of the PSA type can be obtained. In the vertically aligned VA type, a strong vertical alignment force is required in order to generate a vertical alignment. However, this method does not use a polymerizable compound. If the vertical alignment force is increased, the reaction speed after UV irradiation becomes slower. The reaction speed after UV irradiation reduces the vertical alignment force. The vertical alignment force and the increase in the reaction speed after UV irradiation are mutually trade-off. An object of the present invention is to provide a liquid crystal alignment agent which can be used in the same manner as the PSA type by using a liquid crystal which does not contain a polymerizable compound, and can form a liquid crystal alignment film, even in a liquid crystal display which improves the reaction speed after UV irradiation. Among the elements, the vertical alignment force is not lowered, and the reaction speed after UV irradiation can be improved; and a liquid crystal display element having a liquid crystal alignment film obtained by the liquid crystal alignment agent. [Means for Solving the Problem] The gist of the present invention is as follows. [1] A liquid crystal alignment agent comprising the following polyoxyalkylene (A) and 201245334 polyoxyalkylene (B): polyoxyalkylene (A): containing an alkoxydecane represented by the formula (1) And a polyoxyalkylene obtained by polycondensation of an alkoxysilane of an alkoxydecane represented by the formula (2): FMS i (OR2) 3 (1 ) (R1 is a hydrocarbon group which may be substituted by a fluorine atom and has a carbon number of 8 to 30 R2 represents an alkyl group having 1 to 5 carbon atoms. R3S i (0R4) 3 (2) (R3 is an alkyl group having 1 to 30 carbon atoms substituted by an acryl fluorenyl group, a methacryl fluorenyl group or an aryl group, and R4 represents Polyalkylene oxide (B): Polyoxane obtained by polycondensation of alkoxysilane containing 70% to 100% of alkoxysilane represented by formula (3): s ' (OR5) 4 (3) (R5 represents an alkyl group having a carbon number of 1 to 5, [2] The liquid crystal alignment agent of the above [1], wherein the polyfluorene oxide (B Μ is further contained in the formula (2) The polysiloxane which is obtained by the polycondensation of the alkoxy decane of the alkoxy decane. The liquid crystal alignment agent of the above [1], wherein the polyoxane (the oxime system further contains the formula (4) Polycondensation of the alkoxydecane polycondensation of the alkoxydecane represented Oxane: R6S i (0R7) 3 (4) (r6 is an alkyl group having 1 to 5 carbon atoms, and r7 is an alkyl group having a carbon number of i to 5). [4] Any of the above Π]~[3] The liquid crystal alignment agent according to the invention, wherein the polyoxane 201245334 alkane selected from the group consisting of polyoxane (A) and polyoxyalkylene (B) further contains an alkoxy group represented by the following formula (5) Polyoxane obtained by polycondensation of alkoxy alkane of decane. (R8) nS i (OR9) 4-n (5) (R8 is a hydrogen atom or may be a hetero atom, a halogen atom, an amine group or a glycidyl ether a hydrocarbon group having a carbon number of 1 to 12 substituted with a fluorenyl group, a fluorenyl group, an isocyanate group or a ureido group, and an alkyl group having a carbon number of 1 to 5 'n is an integer representing 〇 to 3). [5] As described above] The liquid crystal alignment agent according to any one of the above, wherein the alkoxy decane represented by the above formula (1) contains the alkoxy decane 1 mol% to 20% of the alkoxy oxane used in the polyoxane. The molar %, and the alkoxy decane represented by the above formula (2), contains 10 mol% to 80 mol% of the alkoxy decane represented by the above formula (2). [6] Liquid crystal alignment film, which will be as described in [1]~[5] above A liquid crystal alignment device according to the above [6], which is obtained by applying a liquid crystal alignment agent to a substrate, and drying and firing the liquid crystal display device. [8] A state in which a voltage is applied to a liquid crystal cell in which a liquid crystal cell is sandwiched between two substrates which are fired by the liquid crystal alignment agent according to any one of the above [1] to [5]. Obtained by UV irradiation. [9] A method of producing a liquid crystal display device, which is obtained by applying a liquid crystal alignment agent according to any one of the above [1] to [5], and sandwiching the liquid crystal on the two substrates which are fired, and applying UV is irradiated under voltage conditions. 201245334 [Effects of the Invention] According to the present invention, by using a liquid crystal which does not contain a polymerizable compound and irradiating UV in the same manner as the PSA type, a liquid crystal alignment agent which can be formed without lowering the vertical alignment force can be obtained. A liquid crystal alignment film capable of increasing the reaction rate after UV irradiation; and a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment agent. [Embodiment] <Polyoxalate (A) > Polyoxane (A) is obtained by alkoxy decane containing an alkoxy decane represented by the formula (1) and an alkoxy decane represented by the formula (2) Condensation of the resulting polyoxane. R'S i (OR2) 3 (1) In the formula (1), R1 is a hydrocarbon group which may be substituted by a fluorine atom and has a carbon number of 8 to 30, and R2 represents an alkyl group having 1 to 5 carbon atoms. R3S i (0R4) 3 (2) In the formula (2), R3 is an alkyl group substituted with an acryloyl group, a methacryloyl group or an aryl group, and R4 represents an alkyl group having 1 to 5 carbon atoms. R1 (hereinafter also referred to as a specific organic group) of the alkoxysilane represented by the formula (1) is a hydrocarbon group having a carbon number of 8 to 30 (preferably 8 to 22) which is substituted by fluorine, as long as it has a liquid crystal perpendicular alignment The substance of the effect is not particularly limited. Examples of the specific organic group include an alkyl group, a fluoroalkyl group, an alkenyl group, a phenylethyl group, a styrylalkyl group, a naphthyl group, a fluorophenylalkyl group and the like. Among these, an alkoxydecane wherein R1 is an alkyl group or a fluoroalkyl group is easily obtained as a commercially available product having a lower price, and is therefore suitable. Among the above fluoroalkyl groups, the number of fluorine atoms is -10-201245334 1 or more, and all of the hydrogens may be substituted by fluorine atoms. In particular, it is preferred that the alkoxysilane wherein R1 is an alkyl group. The polyoxyalkylene (A) used in the present invention may also have a plurality of these specific organic groups. R2 of the alkoxydecane represented by the formula (1) has a carbon number of 1 to 5, preferably 1 to 3 alkyl groups. Preferably, R2 is methyl or acetamidine. Specific examples of such alkoxydecane represented by the formula (1) are listed below, but are not limited thereto. For example, octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, decyltriethoxydecane, dodecyltrimethoxydecane, dodecyltriethoxy Decane, cetyltrimethoxydecane, cetyltriethoxydecane, heptadecyltrimethoxydecane, heptadecyltriethoxydecane,octadecyltrimethoxydecane, ten Octaalkyltriethoxydecane, nonadecyltrimethoxynonane, nonadecyltriethoxydecane, undecyltriethoxydecane,undecyltrimethoxydecane,21-di Dodecenyltriethoxydecane, tridecafluorooctyltrimethoxydecane, tridecafluorooctyltriethoxydecane, heptadecafluorodecyltrimethoxydecane, heptadecafluorodecyltriethoxy Decane, isooctyltriethoxydecane, phenethyltriethoxydecane, pentafluorophenylpropyltrimethoxydecane, m-styrylethyltrimethoxydecane, p-styrylethyltrimethoxy Pyridin, (1-naphthyl)triethoxydecane, (bonaphthyl)trimethoxydecane, and the like. Among them, octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, decyltriethoxydecane,dodecyltrimethoxydecane,dodecyltriethoxydecane , cetyltrimethoxydecane, cetyltriethoxydecane, heptadecyltrimethoxydecane, heptadecyltriethoxy-11 - 201245334 decane, octadecyltrimethoxy Decane, octadecyltriethoxydecane, nonadecyltrimethoxydecane, nonadecyltriethoxydecane, undecyltriethoxydecane, or undecyltrimethoxydecane It is better. In order to obtain good liquid crystal alignment, the alkoxysilane represented by the formula U) having the above specific organic group accounts for 1 mole among all the alkoxysilanes used for obtaining the polyoxyalkylene (A). More than % is better. It is preferably 1.5 mol% or more. More preferably 2 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 2 5 mol% or less. R3 (hereinafter also referred to as a second specific organic group) of the alkoxydecane represented by the formula (2) is substituted with at least one selected from the group consisting of an acryloyl group, a methacryl group and an aromatic group. alkyl. The substituted hydrogen atom is preferably one or more. The carbon number of the alkyl group is preferably from 1 to 30, more preferably from 1 to 2 Torr, even more preferably from 1 to 10. The alkyl group may be linear or branched, and is preferably linear. R4 of the alkoxydecane represented by the formula (2) is an alkyl group having 1 to 5 carbon atoms, preferably a carbon number of 1 to 3, particularly preferably a carbon number of 1 to 2. Specific examples of the alkoxydecane represented by the formula (2) are listed below, but are not limited thereto. For example, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, methacryloxymethyltrimethoxydecane, methacrylonitrile Methyl triethoxy decane, 3-propenyl methoxypropyl trimethoxy decane, 3- propylene methoxy propyl triethoxy decane, propylene methoxyethyl trimethoxy decane, propylene oxime Ethyl triethoxy decane, styrylethyl trimethoxy decane, benzene-12- 201245334 vinyl ethyl triethoxy decane, 3-(anthracene acetophenone methyl-2. amine B Amino) propyl trimethoxy decane. In the production of polyoxyalkylene (A), in addition to the oxidized sand enamel represented by the formulas (1) and (2), in order to improve the adhesion to the substrate and the affinity with the liquid crystal molecules, One or more alkoxysilanes represented by the following formula (5) may also be used without impairing the effects of the present invention. The alkoxydecane represented by the formula (5) can impart various properties to the polyoxyalkylene. Therefore, one or more kinds can be selected depending on the necessary characteristics. (R8) nS i (OR9) 4_n (5) In the formula (5), R8 is a hydrogen atom or may be substituted by a hetero atom, a halogen atom, an amine group, a glycidyl ether group, a thiol group, an isocyanate group or a urea group. A hydrocarbon group having 1 to 1 carbon atoms. R9 is an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3). η is an integer of 0 to 3 (preferably 〇~2). R8 of the alkoxysilane represented by the formula (5) is a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 10 (hereinafter also referred to as a third specific organic group). Examples of the third specific organic group, for example, an aliphatic hydrocarbon group; a hydrocarbon group having an aliphatic ring, an aromatic ring, and a heterocyclic ring structure; a hydrocarbon group having an unsaturated bond; and a hetero atom which may contain an oxygen atom, a nitrogen atom, a sulfur atom or the like The atom or the like may have a branched structure and a hydrocarbon group having a carbon number of 1 to 6. The third specific organic group may also be substituted by a dentate atom, an amine group, a glycidyl ether group, a thiol group, an isocyanate group, a urea group or the like. Specific examples of the alkoxysilane represented by the formula (5) are listed below, but are not limited thereto. 3((2-aminoethylaminopropyl)trimethoxydecane, -13- 201245334 3-(2-aminoethylaminopropyl)triethoxydecane, 2-aminoethylaminomethyltrimethyl Oxydecane '2-(2-aminoethylthioethyl)triethoxydecane, 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane, vinyltriethoxydecane, 3-isocyanate propyl triethoxy decane, trifluoropropyl trimethoxy decane, chloropropyl triethoxy decane, bromopropyl triethoxy decane, 3-mercaptopropyl trimethoxy decane, dimethyl Diethoxy decane, dimethyl dimethoxy decane, diethyl diethoxy decane, diethyl dimethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy Decane, 3-aminopropylmethyldiethoxydecane, 3-aminopropyldimethylethoxydecane, trimethylethoxydecane, trimethylmethoxydecane, r-ureidopropyl Ethoxy decane, r-ureidopropyl trimethoxy decane, and r-ureidopropyl tripropoxy decane. In the alkoxydecane represented by the formula (5), an alkoxydecane-based tetradecane decane wherein n is 0. The tetraalkyloxane is easily condensed with the alkoxysilane represented by the formulae (1) to (4), and thus the polyoxyalkylene (the oxime) of the present invention can be obtained, which is suitable. The alkoxy decane wherein η is hydrazine in the formula (5) is preferably tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane or tetrabutoxy decane, especially Oxydecane or tetraethoxydecane is preferred. In the present invention, it is preferable to contain the alkoxy decane represented by the formula (1) in an amount of from 1 to 20 mol%, preferably all of the alkoxy decane used in the production of the polyoxane. It is 2 mol% to 20 mol%, and all alkoxy decane used in the manufacture of polyoxyalkylene (Α) is preferably 10 mol% of the alkoxydecane represented by the formula (2). 80% by mole, especially good for 30% by mole ~ 8 0% by mole. -14 - 201245334 <Polyoxalate (B) > Polyoxane (B) is obtained by polycondensation of alkoxysilane containing 70% by weight to 100% by weight of alkoxysilane represented by formula (3) Polyoxane. S i (〇R5) 4 (3) In the formula (3), R5 represents an alkyl group having 1 to 5 carbon atoms, preferably a carbon number of 1 or 2. A specific example of such an alkoxydecane represented by the formula (3) is preferably tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane or tetrabutoxydecane, particularly tetramethoxy. Preferably, decane or tetraethoxy decane is preferred. The polyoxyalkylene (B) may further be a polyoxyalkylene obtained by polycondensing an alkoxysilane containing an alkoxydecane represented by the formula (2) in addition to the alkoxysilane represented by the formula (3). The alkoxysilane represented by the formula (2) contained in the polyoxyalkylene (B) may be an alkoxysilane used in the production of the above polyoxane (A). The specific examples are also the same as above. The polyoxyalkylene (B) may further be a polyoxyalkylene obtained by polycondensing an alkoxydecane containing an alkoxysilane represented by the formula (4) in addition to the alkoxydecane represented by the formula (3). R6S i (OR,) 3 (4) In the formula (4), R6 is an alkyl group having 1 to 5 carbon atoms, and R7 is an alkyl group having 1 to 5 carbon atoms. R6 of an alkoxydecane represented by the formula (4) It is an alkyl group having 1 to 5 carbon atoms. The carbon number of the alkyl group is preferably from 1 to 4, preferably from 1 to 3. R7 of the alkoxydecane represented by the formula (4) is an alkyl group having 1 to 5 carbon atoms, preferably -15 to 201245334, and a carbon number of 1 to 3, particularly preferably a carbon number of 1 to 2. Specific examples of the alkoxydecane represented by the formula (4) are listed below, but are not limited thereto. For example, methyltriethoxydecane, methyltrimethoxydecane, dimethyltrimethoxydecane, dimethyltriethoxydecane, n-propyltrimethoxydecane, n-propyltriethoxydecane. In particular, the liquid crystal alignment agent further contains a polyoxyalkylene (B) in addition to the alkoxysilane represented by the formula (3), and the polyoxyalkylene (B) is represented by the formula (4). It is obtained by polycondensation of an alkoxydecane alkoxy decane, which has a high vertical alignment force and is particularly suitable. In order to increase the reaction speed of the liquid crystal display element by applying a voltage while applying a voltage to the liquid crystal to which the polymerizable compound is not added, the alkoxysilane represented by the formula (2) having the second specific organic group is used in order to It is preferred that all of the alkoxydecane used in the polyoxyalkylene (B) is 1% by mole or more. It is preferably 20 mol% or more. More preferably 30% or more. Further, in order to sufficiently cure the formed liquid crystal alignment film, it is preferably 75 mol% or less. In the production of the polyoxyalkylene (B), in addition to the alkoxysilane represented by the formula (2), the formula (3), and the formula (4), the adhesion of the substrate and the affinity with the liquid crystal molecules are improved. For the purpose of the present invention, one or more alkoxysilanes represented by the following formula (5) may be used without impairing the effects of the present invention. The alkoxysilane represented by the formula (5) can impart various properties to the polyoxyalkylene, and therefore one or more kinds can be used depending on the necessary characteristics. (R8) nS i (OR9) 4_n (5) In the formula (5), the structures and suitable ranges of R8 and R9, and the formula of the formula (5) are -16-201245334, and the alkoxydecane is specifically described above. <Method for Producing Polyoxane>> The method for obtaining the polyoxyalkylene used in the present invention is not particularly limited. The polyoxyalkylene (A) of the present invention is obtained by polycondensation of an alkoxydecane having an essential component of the above formula (1) and formula (2) in an organic solvent; and polyoxyalkylene (B) is obtained by The above formula (3) is obtained by polycondensation of an alkoxysilane having an essential component in an organic solvent. Usually, polyoxyalkylene is obtained by polycondensing such an alkoxydecane and uniformly dissolving it in an organic solvent to prepare a solution. The method of polycondensing the alkoxydecane may, for example, be a method of hydrolyzing and condensing the alkoxysilane in a solvent such as an alcohol or a glycol. At this time, the hydrolysis and condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add 0.5 times mole of water of all the alkoxy groups in the alkoxysilane, and it is usually preferred to add an excess of 0.5 times mole of water. In the present invention, the amount of water used in the above reaction may be appropriately selected as desired, and it is usually preferably 0.5 times by mole to 2.5 times the mole of all alkoxy groups in the alkoxysilane, and 1 mole of the mole to 2 Double Moore is preferred. Further, in general, in order to promote hydrolysis and condensation reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, citric acid, oxalic acid, maleic acid or fumaric acid may be used; ammonia, methylamine, ethylamine, ethanolamine, triethylamine, etc. A base; a catalyst such as a metal salt such as hydrochloric acid, sulfuric acid or nitric acid. Further, in general, hydrolysis and condensation reaction can be further promoted by heating a solution in which alkoxysilane is dissolved. At this time, the heating temperature and the heating time can be appropriately selected as desired. -17- 201245334, for example, a method of heating at 50 ° C, stirring for 24 hours, heating under reflux, stirring for 1 hour, etc. Further, other methods include, for example, heating a mixture of alkoxysilane, a solvent, and oxalic acid. And the method of making it polycondensed. Specifically, a method in which an oxalic acid alcohol solution is prepared by adding oxalic acid to an alcohol in advance, and then the solution is mixed with an alkoxysilane in a heated state. In this case, the amount of oxalic acid used is preferably 〇 2 mol to 2 mol with respect to 1 mol of all alkoxy groups possessed by the alkoxy decane, and is 0.5 mol to 1.5. Moore is preferred. The heating in this method can be carried out at a liquid temperature of from 50 ° C to 180 ° C in a manner that does not cause liquid evaporation or volatilization, and is heated under reflux for several tens of minutes to several ten hours. In the case where a plurality of alkoxysilanes are used in the case of obtaining a polyoxyalkylene oxide, the alkoxysilane may be mixed in advance to prepare a mixture, or a plurality of alkoxysilanes may be sequentially mixed and used. 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 can dissolve the alkoxysilane. Further, in the case where the alkoxysilane is not dissolved, it may be a substance which can be simultaneously dissolved by the polycondensation reaction. In general, an alcohol is produced by a polycondensation reaction of an alkoxysilane. Therefore, an alcohol, a glycol, a glycol ether, or an alcohol-soluble organic solvent can be used, and a glycol is particularly preferable. Specific examples of such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, and 1,3-propanediol. 1,2-butanediol, 1,3-butane-18-201245334 alcohol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentane Glycols such as diol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol, etc.; Alcohol monomethyl 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, diethyl Diol 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 Glycol ethers such as ether; N-methyl-2-pyrrolidone, N,N-dimethyl Formamide, hydrazine, hydrazine-dimethylacetamide, r-butyrolactone, dimethyl sulfoxide, tetramethyl urea, trimethylamine hexamethylphosphate, m-cresol, and the like. In the present invention, a plurality of the above polymerization solvents may also be used in combination. The polymerization solution (hereinafter also referred to as a polymerization solution) of the polyoxyalkylene obtained by the above method is a concentration obtained by converting the ruthenium atom of all the alkoxysilanes charged as a raw material into Si 〇 2 (hereinafter referred to as Si). It is preferable to set it as 5% by weight to 5% by weight, and it is preferably 5% by weight to 5% by weight. By selecting an arbitrary concentration in this concentration range, the generation of a colloid can be suppressed to obtain a homogeneous solution. <Solution of Polyoxane> In the present invention, the polymerization solution obtained by the above method can be directly used to prepare a solution of polyoxyalkylene. Alternatively, the solution obtained by the above method may be concentrated or added to a solvent to be diluted, or replaced with other dissolved hydrazine to prepare a solution of poly-19-201245334 decane. The solvent (hereinafter also referred to as an additive solvent) used at this time may be the same as the polymerization solvent or may be another solvent. In the case where the polyoxyalkylene is uniformly dissolved, the solvent to be added is not particularly limited, and one or more may be arbitrarily selected and used. Specific examples of such a solvent to be added include, in addition to the solvent exemplified as the above-mentioned polymerization solvent, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methyl acetate and ethyl acetate; An ester such as ethyl lactate. These solvents can adjust the viscosity of the liquid crystal alignment agent or can improve the coatability when the liquid crystal alignment agent is applied onto the substrate by spin coating, offset printing, ink jet or the like. <Other components> In the present invention, other components other than polysiloxane, such as inorganic fine particles and metallooxane, may be contained in the solution of polyoxyalkylene without impairing the effects of the present invention. a component of a polymer, a metal oxyalkylene polymer, a homogenizer, a further surfactant, and the like. The inorganic fine particles are preferably fine particles such as cerium oxide fine particles, alumina fine particles, titanium dioxide fine particles, and magnesium fluoride fine particles, and particularly preferably in the form of a colloidal solution. The colloidal solution may be a solution obtained by dispersing inorganic fine particles in a dispersion medium, or may be a colloidal solution of a commercially available product. In the present invention, by containing inorganic fine particles, the formed hardened film can be given a surface shape and other functions. The average particle diameter of the inorganic fine particles is preferably -20-201245334 Ο.ΟΟΙμιη~0.2μιη, more preferably Ο.ΟΟΙμηι~Ο.ίμηι. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the cured film formed by using the prepared coating liquid may have a decrease in transparency. Examples of the dispersion medium of the inorganic fine particles include water and an organic solvent. The enthalpy or pKa of the colloidal solution is preferably adjusted to 1 to 1 Torr from the viewpoint of the stability of the coating liquid for film formation. It is preferably 2 to 7. Examples of the organic solvent used in the dispersion medium of the colloidal solution include methanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, and ethylene glycol. Alcohols such as propyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N - an amide such as methylpyrrolidone; an ester such as ethyl acetate, butyl acetate or r-butyrolactone; an ether such as tetrahydrofuran or 1,4-dioxane; The ketones are preferred. These organic solvents may be used singly or in combination of two or more kinds as a dispersing medium. As the metal oxyalkylene oligomer and the metal oxyalkylene polymer, a single or composite oxide precursor of ruthenium, titanium, aluminum, ruthenium, osmium, iridium, tin, indium, zinc or the like can be used. The metal oxyalkylene oligomer and the metal oxyalkylene polymer may be commercially available or may be a metal alkoxide, a nitrate, a hydrochloride, a carboxylate or the like, by a conventional method such as hydrolysis. The substance obtained. Specific examples of commercially available metal oxyalkylene oligomers and metalloxane polymers include Methylsilicate 51, Methylsilicate 5 3 A, E thy 1 si 1 icates 40, Ethyl silicates 48, EMS_485, and SS-made by Colcoat. A oxyalkylene oligomer such as 101 or the like, and a titanyl oligomer such as a n-butoxytitanium tetramer manufactured by Kanto Chemical Co., Ltd.. These may be used alone or in combination of two or more. Further, a homogenizing agent, a surfactant, and the like can be used, and it is suitable for use in a commercially available product. Further, the method of mixing the above other components in the polyoxyalkylene can be carried out simultaneously with or after the polyoxyalkylene, and is not particularly limited. [Liquid crystal alignment agent] The liquid crystal alignment agent of the present invention contains the above polyoxyalkylene, and a solution containing other components is necessary. In this case, the solvent may be a solvent selected from the group consisting of a polymerization solvent of the above polyoxyalkylene and a solvent. The content of the per-polysiloxane in the liquid crystal alignment agent is preferably from 5% by weight to 5% by weight, preferably from 1% by weight to 6% by weight, based on the concentration in terms of SiO 2 . As long as such a Si 02 conversion concentration range is obtained, the desired film thickness can be easily obtained in one application, and a sufficient pot life can be easily obtained. The liquid crystal alignment agent of the present invention contains polyoxyalkylene (A) and polyoxyalkylene (B), and the weight ratio of all polyoxyalkylene is 1〇: 90~50: 50 > 20 : 80 ~ 40 : 60. Further, the weight ratio of the per-polyoxyalkylene to the other components to be added in the liquid crystal alignment agent of the present invention is 99:1 to 50:50, preferably 98:2 to 70:30. 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 -22-201245334 parts which are necessary to be added. Usually, the polyoxyalkylene is dissolved, so that a simple method is to directly use a solution of polyoxyalkylene in a solution of a decane which is necessary to add other components. Further, the method of directly using the polymerization solution of polyoxyalkylene is the easiest. Further, the polyoxosiloxane in the liquid crystal alignment agent is adjusted to contain a solvent selected from the group consisting of a polymerization solvent of the alkoxysilane and a polyoxyalkylene. [Liquid Crystal Alignment Film] The liquid crystal alignment film of the present invention is obtained by using the liquid crystal of the present invention. 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. Further, the cured film may be subjected to rubbing, irradiation of light or light, or the like, or treatment with an ion beam or the like, or irradiation of UV in a state where a voltage is applied to the liquid crystal display element. The substrate to which the liquid crystal alignment agent is applied is particularly limited as long as it has high transparency, and a substrate for driving the liquid crystal electrode is preferably formed on the substrate. Specific examples thereof include glass plates, polycarbo (meth) acrylates, polyether oximes, polyarylates, urethanes, polyethers, polyether ketones, trimethylpentene, and polyolefins. A method for coating a transparent electrode liquid crystal alignment agent such as a plastic plate such as polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diethylbenzene or cellulose acetate butyrate, and examples thereof include a spin coating agent. In the case of polycondensation, or in the case of agglomeration, a solvent-aligning agent may be added, and then the alignment film may be subjected to a specific wavelength, and the substrate after the specific wavelength is not added is a transparent acid ester, a polyethylene ester, or a polyphthalic acid-based base. The substrate of the fiber. Method, printing -23-201245334 Method, inkjet method, spray method, light coating method, etc., and from the viewpoint of productivity, a transfer method widely used in the industry is also suitable for use in the present invention. After the liquid crystal alignment agent is applied, the drying step is not necessarily required, and the time from the application to the time when the firing is stopped varies with each substrate, or the case where the firing is not immediately performed after the coating is performed, good. This drying is not limited to the extent that the shape of the coating film is not deformed by the conveyance of the substrate or the like, and the solvent can be removed. The drying means is not particularly limited. For example, it can be dried on a hot plate at a temperature of 40 ° C to 150 ° C (preferably 60 ° c to 100 ° C) for 5 minutes to 30 minutes (preferably 1 minute to 5 minutes). method. 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 can be carried out at any temperature of 100 ° C to 35 (TC, preferably 140 ° C to 300 ° C ^ preferably 150 ° C to 23 0 ° C, more preferably 160 ° C ～220° C. The firing time can be calcined at any time from 5 minutes to 240 minutes, preferably from 10 minutes to 90 minutes, preferably from 20 minutes to 80 minutes. Heating is usually carried out using a known method such as a hot plate. , a hot air circulation oven, an IR (infrared) oven, a belt furnace, etc. The polyoxyalkylene in the liquid crystal alignment film is subjected to polycondensation in the firing step. However, in the present invention, the effect of the present invention is not impaired. On the premise, it is not necessary to completely condense it, but it is preferably burned at a temperature higher than the heat treatment temperature of the sealing agent hardening required for the liquid crystal cell manufacturing step, etc. The thickness of the cured film can be necessary. Preferably, it is preferably 5 nm or more, preferably 10 nm or more, and is suitable because it can easily obtain the reliability of the liquid crystal display element -24-201245334. Further, the thickness of the cured film is preferably 3 OOnrr or less. Below 150nm, due to the consumption of liquid crystal display elements It does not become great, and therefore is suitable. <Liquid Crystal Display Element> The liquid crystal display element of the present invention can be obtained by forming a liquid crystal cell by a known method after forming a liquid crystal alignment film on a substrate by the above method. In the case of an example of the production of the liquid crystal cell, there is generally a method in which a spacer is sandwiched between a pair of substrates on which a liquid crystal alignment film is formed, and is fixed by a sealant, and liquid crystal is injected and sealed. At this time, the size of the spacer to be used is Ιμιη~30μηι, and preferably 2μηι 〜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 decompressed in the produced liquid crystal cell, and a liquid drop method in which a liquid crystal is dropped after the liquid crystal is dropped. When UV is applied between the electrodes of the substrates on both sides of the liquid crystal cell into which the liquid crystal is introduced, the acryl fluorenyl group, the methacryl fluorenyl group or the like in the alignment film is polymerized and crosslinked, and the liquid crystal is crosslinked. The response speed of the display becomes faster. Here, the applied voltage is 5Vp-p to 50Vp-p, and preferably 5Vp-p to 30Vp-p. The amount of UV irradiation to be irradiated is 1 J (joules) to 60 J, and preferably 40 J or less. When the amount of the UV irradiation is small, it is possible to suppress the decrease in the reliability (the characteristic that the members constituting the liquid crystal display is not broken) and to reduce the U V irradiation time & the production cycle (work amount) is improved. The substrate used in the liquid crystal display device is not particularly limited as long as it is a highly transparent substrate, and a substrate having a transparent electrode for driving liquid crystal at -25 - 201245334 is usually formed on the substrate. The specific example is the same as the substrate described in [Liquid Crystal Alignment Film]. A substrate having an electrode pattern or a protrusion pattern such as a so-called PVA or MVA can also be used. In the substrate used for the liquid crystal display device, a line width/slit electrode pattern of 1 μm to 1 μm is formed on the single-sided substrate in the same manner as the PSA liquid crystal display, and no slit pattern or protrusion is formed on the opposite substrate. The structure of the pattern can also be operated. With the liquid crystal display thus constructed, the program at the time of manufacture can be simplified, and high transmittance can be obtained. Further, among the high-performance liquid crystal display elements such as the TFT type liquid crystal display element, a transistor element may be formed on the substrate between the electrode for driving the liquid crystal and the substrate. In the case of a transmissive liquid crystal display device, a substrate as described above is generally used, and in the reflective liquid crystal display device, a material such as aluminum which reflects light only on one side substrate may be used, or a germanium wafer or the like may be used. Opaque substrate. [Examples] Hereinafter, the present invention will be further specifically described by way of Examples, but the present invention is not construed as limited thereto. Abbreviations for the compounds used in this example are as follows. TEOS: tetraethoxydecane C18: octadecyltriethoxydecane ACPS: 3-propenyloxypropyltrimethoxydecane MPMS: 3-methylpropenyloxypropyltrimethoxydecane-26 - 201245334 MTES: methyltriethoxydecane HG: 2-methyl-2,4-pentanediol (alias: hexanediol) BCS: 2-butoxyethanol UPS: 3-ureidopropyltriethoxy Base decane <Synthesis Example 1 > In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 20.6 g of HG, 6.9 g of BCS, 18.3 g of TEOS, 4.2 g of C18, and 23.4 g of ACPS were mixed to prepare A solution of alkoxyoxane monomer. In this solution, a solution obtained by mixing 10.3 g of HG, 3.4 g of BCS, 1 g of water, and 1.4 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes. It was further stirred at room temperature for 30 minutes. Then, the mixture was heated in an oil bath and refluxed for 30 minutes, and then a mixed liquid obtained by previously mixing a methanol solution having a UPS content of 92% by mass, 6 g, 0.3 g of HG, and O.lg, BCS was added. Further, it was refluxed for 30 minutes and then allowed to cool to obtain a polyoxydeoxygenane solution having a concentration of SiO 2 of 12% by weight. The obtained polyaluminoxane solution 10 〇g was mixed with 20.0 g of BCS to obtain a liquid crystal alignment agent intermediate (S1) having a SiO 2 conversion concentration of 4% by weight. Further, 23.6 g of HG, 7-9 g of BCS and 41.2 g of TEOS were mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube to prepare a solution of the alkoxysilane monomer. In this solution, a solution obtained by mixing 1 1.8 g of HG, 3.9 g of -27-201245334 BCS, 10.8 g of water' and 0.2 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes. It was further stirred at room temperature for 30 minutes. Then, the mixture was heated in an oil bath and refluxed for 30 minutes, and then a mixed liquid obtained by mixing a methanol solution having a UPS content of 92% by mass in 甲醇6 g, 0.3 g of HG and O.lg of BCS was added. Further, it was refluxed for 30 minutes and then allowed to cool to obtain a polyoxane solution having a SiO 2 conversion concentration of 12% by weight. The obtained polyoxane solution l〇.〇g was mixed with 2〇.〇g of BCS to obtain a liquid crystal alignment agent intermediate (U 1)» in a concentration of 4% by weight in Si 02 . The liquid crystal alignment agent intermediate (s 1) and the liquid crystal alignment agent intermediate (u 1) are mixed at a ratio of 3:7 (weight ratio 'the same as the following') to obtain a liquid crystal alignment agent having a SiO 2 conversion concentration of 4% by weight [K1]. . <Synthesis Example 2 > In a 20 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 19.9 g of HG, 6.6 g of BCS, 18.3 g of TEOS, 4.2 g of C18, and 24.8 g of MPMS were mixed. Prepare a solution of the discharged oxygen sand sputum monomer. In this solution, a solution obtained by mixing lO.Og of HG, 3.3 g of BCS, 10.8 g of water, and 1.4 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes. Stir at room temperature for 30 minutes. Then, the mixture was heated in an oil bath to be refluxed for 30 minutes, and a mixed liquid obtained by mixing 0.6 g of a methanol solution having a UPS content of 92% by mass, 〇3 g of HG, and O.lg of BCS was added. Further, it was refluxed for 30 minutes and then allowed to cool to obtain a polyoxaxane solution having a Si 2 concentration of 12% by weight. -28-201245334 10.0 g of the obtained polyoxyalkylene solution and 20.0 g of B C S were mixed to obtain a liquid crystal alignment agent intermediate (S2) having a concentration of SiO 2 of 4% by weight. The obtained liquid crystal alignment agent intermediate (S2) and the liquid crystal alignment agent intermediate (U1) obtained in Synthesis Example 1 were mixed at a ratio of 3:7 to obtain a liquid crystal alignment agent having a concentration of SiO 2 of 4% by weight. K2]. <Synthesis Example 3 > In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 23.3 g of HG, 7.8 g of BCS, 39.2 g of TEOS, and 2.5 g of MPMS were mixed to prepare an alkoxydecane single Body solution. In this solution, a solution obtained by mixing 11.7 g of HG' 3.9 g of BCS, 10.8 g of water, and 0.4 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes, and further at room temperature. Stir for 30 minutes. Then, the mixture was refluxed for 30 minutes using an oil bath, and then a mixed liquid obtained by mixing a methanol solution having a UPS content of 92% by mass in 66 g, 0.3 g of HG and O.lg of BCS was added. Further, it was refluxed for 30 minutes and then allowed to cool to obtain a polyoxane solution having a SiO 2 conversion concentration of 12% by weight. The obtained polyoxysilane solution l〇.〇g was mixed with 20.0 g of BCS to obtain a liquid crystal alignment agent intermediate (U2) having a concentration of SiO 2 of 4% by weight. The liquid crystal alignment agent intermediate (U2) obtained by the liquid crystal alignment agent intermediate (S1) obtained in Synthesis Example 1 was mixed at a ratio of 3:7 to obtain a liquid crystal alignment agent having a concentration of SiO 2 of 4% by weight [K3 ] » <Synthesis Example 4 > -29 - 201245334 The liquid crystal alignment agent intermediate (S2) obtained in Synthesis Example 2 and the liquid crystal alignment agent intermediate (U2) obtained in Synthesis Example 3 were mixed at a ratio of 3:7. A liquid crystal alignment agent [K4] having a Si02 conversion concentration of 4% by weight was obtained. <Synthesis Example 5 > In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 23.8 g of NG, 7.9 g of BCS, 37.1 g of TEOS, and 3.6 g of MTES were mixed to prepare an alkoxydecane single Body solution. In this solution, a solution obtained by mixing 11.9 g of HG, 4.0 g of BCS, 10.8 g of water, and 0.4 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes, and further at room temperature. Stir for 30 minutes. Then, the mixture was heated in an oil bath and refluxed for 30 minutes, and then a mixed liquid obtained by mixing a UPS content of 92% by mass of methanol solution 〇6 g, 0.3 g of HG and O.lg of BCS was added. Further, it was refluxed for 30 minutes and then allowed to cool to obtain a polyoxane solution having a Si?2 conversion concentration of 12% by weight. The obtained polyoxane solution l〇.〇g was mixed with 20.0 g of BCS to obtain a liquid crystal alignment agent intermediate (U3) having a Si〇2 conversion concentration of 4% by weight. The liquid crystal alignment agent intermediate (S1) and the obtained liquid crystal alignment agent intermediate (U 3 ) were mixed at a ratio of 3:7 to obtain a liquid crystal alignment agent [K5] having a SiO 2 conversion concentration of 4% by weight. <Synthesis Example 6 > The liquid crystal alignment agent intermediate (S2) obtained in Synthesis Example 2 - the liquid crystal alignment agent intermediate (U3) obtained in Synthesis Example 5 was mixed at a ratio of 3:7, -30 - 201245334 A liquid crystal alignment agent having a Si〇2 conversion concentration of 4% by weight was obtained [Κ6] » <Comparative Synthesis Example 1 > In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 22.6 g of HG, 7.5 g of BCS, and 39.6 g of TEOS were mixed to prepare a solution of an alkoxysilane monomer. In this solution, a solution obtained by mixing 11.3 g of HG, 3.8 g of BCS, 10.8 g of water, and 0.2 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes, and further at room temperature. Stir for 30 minutes. Then, it was heated in an oil bath, refluxed for 1 hour, and then allowed to cool to obtain a polyoxysilane solution having a SiO 2 conversion concentration of 12% by weight. The obtained polyoxydecane solution 10. 〇g was mixed with 20.0 g of BCS to obtain a liquid crystal alignment agent [L 1 ] having a SiO 2 conversion concentration of 4% by weight. <Comparative Synthesis Example 2 > A liquid crystal alignment agent [L2] was obtained in the same manner as in the liquid crystal alignment agent intermediate (S1) obtained in Synthesis Example 1. <Comparative Synthesis Example 3 > A liquid crystal alignment agent [L3] was obtained in the same manner as in the liquid crystal alignment agent intermediate (S2) obtained in Synthesis Example 2. <Example 1> The liquid crystal alignment treatment agent [K1] obtained in Synthesis Example 1 was spin-coated on the ITO surface of the -31 - 201245334 ITO electrode substrate having a pixel size of 100 μm X 3 00 μm. The line width/pitch is a 5 micron ΙΤΟ electrode pattern. After drying at 80 ° C for 2 minutes, the film was fired in a hot air circulating oven at 200 ° C or 220 t for 30 minutes to form a liquid crystal alignment film having a film thickness of 10 nm. The liquid crystal alignment treatment agent [K1] obtained in Synthesis Example 1 was spin-coated on an ITO surface which was not formed into an electrode pattern, and dried on a hot plate at 80 ° C for 2 minutes, and then 200 ° C in the same manner as the above substrate. Or a hot air circulating oven of 220 ° C was baked for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. After preparing such two substrates, a 6 μηη bead spacer was spread on the liquid crystal alignment film surface of one of the substrates, and then a sealant was printed thereon. After the other substrate is bonded to the inner side of the liquid crystal alignment film surface, the sealing agent is cured to form an empty space. Liquid crystal MLC-6608 (trade name, manufactured by Merck Co., Ltd.) was injected into an empty space by a pressure reduction injection method to prepare a liquid crystal cell. The reaction rate characteristics of the obtained liquid crystal cell were measured by the method described later. Then, in the liquid crystal cell, 20 Vp-p was applied with a voltage, and thus the outside of the liquid crystal cell was irradiated with UV (using a band pass filter having a wavelength of 365 nm) 2 〇 J. Then, the reaction rate characteristics were measured again, and the reaction rates before and after the UV irradiation were compared. Reveal the results in the table! . Further, the vertical alignment of the groove is also measured and evaluated by the method described later. The results are disclosed in Table 1. <Example 2> A liquid crystal was produced in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [K 1 ] was changed to the -32-201245334 liquid crystal alignment treatment agent [K2] obtained in Synthesis Example 2. Groove and measure the reaction rate. The results are disclosed in Table 1. <Example 3> A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [Κ1] was changed to the liquid crystal alignment treatment agent [Κ3] obtained in Synthesis Example 3, and the reaction was measured. speed. The results are disclosed in Table 1. <Example 4> A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [Κ1] was changed to the liquid crystal alignment treatment agent [Κ4] obtained in Synthesis Example 4, and the reaction was measured. speed. The results are disclosed in Table 1. <Example 5> A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [Κ1] was changed to the liquid crystal alignment treatment agent [Κ5] obtained in Synthesis Example 5, and the reaction was measured. speed. Reveal the results in Table 1 » <Example 6> A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [Κ1] was changed to the liquid crystal alignment treatment agent [Κ6] obtained in Synthesis Example 6, and the reaction was measured. speed. The results are disclosed in Table 1. <Comparative Example 1 > -33-201245334 A liquid crystal alignment treatment agent [κ1] was changed to the liquid crystal alignment treatment agent [L1] obtained in Comparative Synthesis Example 1, and was produced in the same manner as in Example 1. The liquid crystal cell was measured and the reaction rate was measured. Reveal the results in the table <Comparative Example 2> A liquid crystal cell was produced and measured in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [Κ1] was changed to the liquid crystal alignment treatment agent [L2] obtained in Comparative Synthesis Example 2. reaction speed. Reveal the results in the table <Comparative Example 3> A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [Κ1] was changed to the liquid crystal alignment treatment agent [L3] obtained in Comparative Synthesis Example 2, and the reaction was measured. speed. The results are disclosed in the table. [Reaction Velocity Characteristics] When a square wave having a voltage of ±4 V and a frequency of 1 kHz is applied to a liquid crystal cell to which no voltage is applied, a change in luminance of the liquid crystal panel with time is recorded in the oscilloscope. The luminance when no voltage is applied is set to 0%, the luminance of saturation is set to 100% when a voltage of ±4 V is applied, and the time when the luminance is changed from 10% to 90% is determined as the rising reaction rate. -34- 201245334 [Vertical Alignment] The evaluation of the vertical alignment is performed by arranging a groove between two polarizing plates arranged in orthogonal polarized light, and judging whether or not a black display is displayed. The more the vertical alignment is exhibited, the higher the vertical alignment. [Table 1]
UV照射前之 反應速度(ms) UV照射後之 反應速度(ms) 垂直配 向性 200°C燒成 220°C燒成 實施例1 >700 39 〇 〇 實施例2 >700 25 〇 〇 實施例3 >700 37 〇 〇 實施例4 >700 28 〇 〇 實施例5 >700 43 〇 ◎ 實施例6 >700 29 〇 ◎ 比較例1 >700 >700 〇 〇 比較例2 >700 41 〇 X 比較例3 >700 26 〇 X X:並未表現出垂直配向 〇：在200°c或220°c 30分鐘的燒成中表現出垂直配向 ◎:在22CTC、60分鐘的燒成中亦表現出垂直配向 由表1可知，在實施例之液晶槽的情況，在220°C燒 成時會表現出垂直配向，且UV照射後反應速度提升。尤 其是實施例5與實施例6之液晶槽，在220 °C燒成的時間 延至60分鐘時，亦表現出垂直配向。另一方面，在比較 例1的情況，在220°C燒成時會表現出垂直配向，而在 -35- 201245334 UV照射後，反應速度並未提升。在比較例2、3的情況， 在UV照射之後反應速度提升，然而在2 20 °C燒成時並未 表現出垂直配向。 產業上之可利用性 使用本發明之液晶配向劑所製作出的液晶顯示元件， 在PSA型的配向方式中，即使在使用不添加聚合性化合 物的液晶的情況下，仍可提供能夠得到與PSA型同等特 性的液晶顯示元件，而能夠使用作爲PSA型TFT液晶顯 示元件、TN液晶顯示元件、VA液晶顯示元件等。 此外’將201 1年2月24日申請的日本專利申請 2〇 1 1 -3 84 1 3號說明書、申請專利範圍及發明摘要的全部 內容引用於此，收編爲本發明說明書的揭示。 -36-Reaction rate before UV irradiation (ms) Reaction rate after UV irradiation (ms) Vertical alignment 200 ° C firing 220 ° C firing Example 1 > 700 39 〇〇 Example 2 > 700 25 〇〇 Implementation Example 3 > 700 37 〇〇 Example 4 > 700 28 〇〇 Example 5 > 700 43 〇 ◎ Example 6 > 700 29 〇 ◎ Comparative Example 1 > 700 > 700 〇〇 Comparative Example 2 > ;700 41 〇X Comparative Example 3 > 700 26 〇 XX: No vertical alignment 〇: Vertical alignment at 200 ° C or 220 ° C for 30 minutes of firing ◎: burning at 22 CTC, 60 minutes In the case of the liquid crystal cell of the example, in the case of the liquid crystal cell of the example, the vertical alignment is exhibited at the time of firing at 220 ° C, and the reaction speed after UV irradiation is increased. In particular, the liquid crystal cells of Example 5 and Example 6 exhibited a vertical alignment when the firing time at 220 ° C was extended to 60 minutes. On the other hand, in the case of Comparative Example 1, the vertical alignment was exhibited at 220 ° C, and the reaction rate was not improved after -35 - 201245334 UV irradiation. In the case of Comparative Examples 2 and 3, the reaction speed was increased after the UV irradiation, but the vertical alignment was not exhibited at the firing at 2 20 °C. INDUSTRIAL APPLICABILITY A liquid crystal display device produced by using the liquid crystal alignment agent of the present invention can provide a PSA capable of obtaining a PSA type alignment method even when a liquid crystal containing no polymerizable compound is used. A liquid crystal display element having the same characteristics can be used as a PSA type TFT liquid crystal display element, a TN liquid crystal display element, a VA liquid crystal display element, or the like. In addition, the entire contents of the specification, the scope of the patent application, and the abstract of the disclosure of the Japanese Patent Application No. -36-