[實施發明之最佳形態] [0024] 以下，對於本發明之實施形態進行詳細說明。 本發明之液晶配向劑，其係含有由二胺成分與酸二酐成分所得之聚合物(以下，亦稱為特定聚合物，或亦稱為主鏈型高分子)之液晶配向劑，該二胺成分包含上述式(1)所表示之二胺，該酸二酐成分包含上述式(2)所表示之四羧酸二酐。以下對於各條件來進行詳述。 [0025] ＜具有特定構造之二胺＞ 本發明之液晶配向劑，其係含有聚合物與有機溶劑之液晶配向劑，該聚合物係由二胺成分與酸二酐成分所得，該二胺成分包含式(1)所表示之二胺(本發明中亦稱為特定二胺)，該酸二酐成分包含式(2)所表示之四羧酸二酐(本發明中亦稱為特定四羧酸二酐)。 [0026][0027] 式(1)中，L係碳數2以上的二價有機基且同時包含伸烷基、與選自醚鍵及酯鍵之鍵結中之任1種，R1
及R2
係分別獨立為一價有機基，p1及p2係分別獨立為0~4的整數，p係0或1，q1及q2係分別獨立為1或2。 [0028] 作為於此之一價有機基，可舉出具有碳數1~10(較佳為1~3)的烷基、烯基、烷氧基、氟烷基、氟烯基、或氟烷氧基。其中，作為一價有機基係以甲基為較佳。 [0029] 作為二價有機基，可舉出：以伸烷基與醚鍵所構成的基、或以伸烷基與酯鍵所構成的基、氫原子的一部分或全部被鹵素所取代的以伸烷基與醚鍵所構成的基、或氫原子的一部分或全部被鹵素所取代的以伸烷基與酯鍵所構成的基。其中，作為二價有機基係以伸烷基與醚鍵所構成的基為較佳。碳數係以2以上20以下者為較佳，以2以上10以下者為又較佳。 [0030] 又，L的原子數之中，與主鏈的長度有關的碳原子和氧原子的原子數的合計若為偶數之情形時，所得之聚合物之直線性會變高，其結果，於偏光照射後之加熱步驟中，藉由更高秩序地進行再配向，而可得到賦予高配向控制能的液晶配向膜，故為較佳。尚，與主鏈的長度有關的碳原子和氧原子的原子數的合計，係指將主鏈的每一個亞甲基的數設為1，將每一個醚鍵的數設為1，將每一個酯鍵的數設為2時的合計。 [0031] 作為p1及p2，就立體阻礙少而苯基彼此容易重疊、並以更高秩序地進行再配向之點而言，以0為較佳。 作為p，就具有作為自由旋轉部位功能的伸烷基能以更高秩序地進行再配向之點而言，以1為較佳。 上述式(1)之二胺中，作為p為1之二胺之具體例係可示例如下，但並非限定於該等。 [0032][0033][0034][0035] 於此，若r、t及u的合計為2、4、6、8及10等的偶數之情形時，所得之聚合物之直線性會變高，其結果，於偏光照射後之加熱步驟中，藉由更高秩序地進行再配向，而可得到賦予高配向控制能的液晶配向膜。 s為1、3、5等的奇數，但依上述之理由為較佳。 上述式(1)所表示之二胺之中，作為p為0之二胺之具體例，可舉出p-苯二胺。 [0036] ＜聚合物＞ 本發明之聚合物，其係由二胺成分與酸二酐成分所得之聚合物，該二胺成分包含上述式(1)所表示之二胺，該酸二酐成分包含上述式(2)所表示之四羧酸二酐。 作為具體例，可舉出聚醯胺酸、聚醯胺酸酯、聚醯亞胺、聚脲、聚醯胺等，但就作為液晶配向劑使用之觀點而言，以選自包含下述式(3)所表示之構造單位之聚醯亞胺前驅物、及該醯亞胺化物的聚醯亞胺之至少1種為較佳。於偏光照射後的加熱步驟中，就在聚合物中自由旋轉部位越多可更高秩序地進行再配向之點而言，以聚醯亞胺前驅物為又較佳。 [0037][0038] 上述式(3)中，X1
係源自上述式(2)所表示之四羧酸衍生物之四價有機基，Y1
係源自包含式(1)的構造之二胺之二價有機基，R11
係氫原子或碳數1~5的烷基。就容易藉由加熱而醯亞胺化之點而言，R11
係以氫原子、甲基或乙基為較佳，以氫原子為又較佳。 [0039] ＜四羧酸二酐＞ X1
係源自上述式(2)所表示之四羧酸衍生物之四價有機基。 式(2)中，R6
~R9
係分別獨立為氫原子、烷基、鹵素原子或苯基 下述構造之中，就液晶配向性之觀點而言，以R6
~R9
為氫原子者為較佳。 [0040][0041] ＜二胺＞ 式(3)中，作為Y1
之具體例可舉出由前述式(1)之二胺中除去2個胺基而成之構造。其中，以由上述較佳的二胺中除去2個胺基而成之構造為較佳。 [0042] ＜聚合物(其他的構造單位)＞ 包含式(3)所表示之構造單位之聚醯亞胺前驅物，在不損及本發明之效果之範圍內，亦可包含選自下述式(4)所表示之構造單位、及該醯亞胺化物的聚醯亞胺之至少1種。 [0043][0044] 式(4)中，X2
為源自四羧酸衍生物之四價有機基，Y2
係源自二胺之二價有機基，R12
係與前述式(3)之R11
的定義為相同，R22
係表示氫原子或碳數1~4的烷基。又，2個R22
之至少一者係以氫原子為較佳。 X2
係源自四羧酸衍生物之四價有機基，其構造並無特別限定。又，聚醯亞胺前驅物中之X2
係因應聚合物對溶劑之溶解性或液晶配向劑之塗佈性、製成液晶配向膜時之液晶的配向性、電壓保持率、儲存電荷等所需要的特性之程度來做適當選擇，在相同聚合物中可存在1種類、或亦可混合存在2種類以上。 [0045] 若要表示X2
之具體例時，可舉出國際公開公報2015/119168的第13~14頁所刊載之式(X-1)~(X-46)之構造等。 以下雖表示較佳的X2
之構造，但本發明並非被限定於該等。 [0046][0047][0048] 又，聚醯亞胺前驅物中之Y2
係源自二胺之二價有機基，其構造並無特別限定。又，Y2
係因應聚合物對溶劑之溶解性或液晶配向劑之塗佈性、製成液晶配向膜時之液晶的配向性、電壓保持率、儲存電荷等所需要的特性之程度來做適當選擇，在相同聚合物中可存在1種類、或亦可混合存在2種類以上。 [0049] 若要表示Y2
之具體例時，可舉出國際公開公報2015/119168的第4頁所刊載之式(2)之構造、及第8~12頁所刊載之式(Y-1)~(Y-97)、(Y-101)~(Y-118)之構造；國際公開公報2013/008906第6頁所刊載之由式(2)中除去2個胺基而成之二價有機基；國際公開公報2015/122413的第8頁所刊載之由式(1)中除去2個胺基而成之二價有機基；國際公開公報2015/060360的第8頁所刊載之式(3)之構造；日本國公開專利公報2012-173514的第8頁所刊載之由式(1)中除去2個胺基而成之二價有機基；國際公開公報2010-050523第9頁所刊載之由式(A)~(F)中除去2個胺基而成之二價有機基等。 [0050] 作為較佳的Y2
之構造，可舉出下述式(5)之構造。尚，Y2
之構造可為源自特定二胺(1)之構造也無妨。 [0051][0052] 式(5)中，R32
係單鍵或二價有機基，以單鍵為較佳。 R33
係-(CH2
)n
-所表示之構造。n係2~10的整數，以3~7為較佳。又，任意的-CH2
-係以分別不鄰接之條件下，亦可被醚、酯、醯胺、脲、胺甲酸酯鍵所取代。 R34
係單鍵或二價有機基。 苯環上之任意的氫原子係亦可以一價有機基所取代，以氟原子或甲基為較佳。 作為式(5)所表示之構造，具體而言可舉出如以下般的構造，但並非被限定於該等。 [0053][0054][0055][0056][0057][0058] 其中，就不阻礙選自包含式(3)所表示之構造單位之聚醯亞胺前驅物、及該醯亞胺化物的聚醯亞胺之至少1種的再配向之點而言，以包含與特定二胺(1)共通的部分構造者為較佳。 [0059] 包含式(3)所表示之構造單位之聚醯亞胺前驅物，若同時包含式(4)所表示之構造單位之情形時，式(3)所表示之構造單位相對於式(3)與式(4)的合計以30莫耳%~100莫耳%為較佳，又較佳為50莫耳%~100莫耳%，特佳為70莫耳%~100莫耳%。 [0060] 本發明中使用之聚醯亞胺前驅物的分子量係以重量平均分子量為2,000~500,000為較佳，又較佳為5,000~300,000，更佳為10,000~100,000。 作為本發明中使用之聚醯亞胺，可舉出使前述之聚醯亞胺前驅物閉環而得到的聚醯亞胺。該聚醯亞胺中，醯胺酸基的閉環率(亦稱為醯亞胺化率)不一定需要100%，可依據用途或目的來任意地調整。關於本發明之聚合物，就液晶配向性之觀點而言，醯亞胺化率係以0~70%為較佳，又較佳為0~50%。 作為使聚醯亞胺前驅物醯亞胺化之方法，可舉出將聚醯亞胺前驅物的溶液直接加熱之熱醯亞胺化、或添加觸媒至聚醯亞胺前驅物的溶液中之觸媒醯亞胺化。 [0061] ＜液晶配向劑＞ 本發明之液晶配向劑係含有由二胺成分與酸二酐成分所得之聚合物(特定聚合物)，該二胺成分包含上述式(1)所表示之二胺，該酸二酐成分包含上述式(2)所表示之四羧酸二酐，但在可發揮本發明所記載的效果之限度內，亦可含有2種以上不同構造的特定聚合物。又，除了特定聚合物之外，亦可含有其他的聚合物，即，不具有源自式(1)所表示之二胺之二價的基之聚合物。作為其他的聚合物的種類，可舉出聚醯胺酸、聚醯亞胺、聚醯胺酸酯、聚酯、聚醯胺、聚脲、聚有機矽氧烷、纖維素衍生物、聚縮醛、聚苯乙烯或其衍生物、聚(苯乙烯-苯基馬來醯亞胺)衍生物、聚(甲基)丙烯酸酯等。本發明之液晶配向劑若含有其他的聚合物之情形時，相對於全聚合物成分之特定聚合物的比例係以10質量%以上為較佳，作為其一例子可舉出為10~100質量%。 [0062] 液晶配向劑係用於製作液晶配向膜而被使用，就可形成均勻的薄膜之觀點而言，一般為採用塗佈液之形態。即使是本發明之液晶配向劑，亦以含有前述之聚合物成分、與使該聚合物成分溶解之有機溶劑之塗佈液為較佳。此時，液晶配向劑中之聚合物的濃度係可依據想要形成的塗膜的厚度設定來做適當變更。就形成均勻且無缺點的塗膜之點而言，以1質量%以上為較佳，就溶液的保存穩定性之點而言，以設為10質量%以下為較佳。特佳的聚合物的濃度為2~8質量%。 [0063] 液晶配向劑中所含有的有機溶劑只要是能均勻溶解聚合物成分者即可並無特別限定。若舉出其具體例時，可舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、二甲基亞碸、γ-丁內酯、1,3-二甲基-咪唑啉酮、甲基乙基酮、環己酮、環戊酮等。其中，以使用N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、或γ-丁內酯為較佳。 [0064] 又，液晶配向劑中所含有的有機溶劑除了如上述般的溶劑之外，通常可以併用使塗佈液晶配向劑時的塗佈性或塗膜的表面平滑性提升之溶劑的混合溶劑來使用，即使是本發明之液晶配向劑，亦可適合使用如此般的混合溶劑。將併用的有機溶劑之具體例可舉出於下述，但並非被限定於該等之例子。 [0065] 可舉出例如乙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、tert-丁醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊醇、tert-戊醇、3-甲基-2-丁醇、新戊醇、1-己醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己醇、1,2-乙二醇、1,2-丙二醇、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、1,5-戊二醇、2-甲基-2,4-戊二醇、2-乙基-1,3-己二醇、二丙基醚、二丁基醚、二己基醚、二噁烷、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚、1,2-丁氧基乙烷、二乙二醇二甲基醚、二乙二醇二乙基醚、4-羥基-4-甲基-2-戊酮、二乙二醇甲基乙基醚、二乙二醇二丁基醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、3-乙氧基丁基乙酸酯、1-甲基戊基乙酸酯、2-乙基丁基乙酸酯、2-乙基己基乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、碳酸伸丙酯、碳酸伸乙酯、2-(甲氧基甲氧基)乙醇、乙二醇單丁基醚、乙二醇單異戊基醚、乙二醇單己基醚、2-(己氧基)乙醇、糠醇、二乙二醇、丙二醇、丙二醇單丁基醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲基醚乙酸酯、二丙二醇、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇二甲基醚、三丙二醇單甲基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、2-(2-乙氧基乙氧基)乙基乙酸酯、二乙二醇乙酸酯、三乙二醇、三乙二醇單甲基醚、三乙二醇單乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯、下述式[D-1]~[D-3]所表示之溶劑等。 [0066][0067] 式[D-1]中，D1
係表示碳數1~3的烷基，式[D-2]中，D2
係表示碳數1~3的烷基，式[D-3]中，D3
係表示碳數1~4的烷基。 [0068] 如此般的溶劑的種類及含有量係可因應液晶配向劑的塗佈裝置、塗佈條件、塗佈環境等來做適當選擇。 [0069] 本發明之液晶配向劑，在不損及本發明之效果的範圍內，亦可追加含有除了聚合物成分及有機溶劑以外的成分。作為如此般的追加成分，可舉出用於使液晶配向膜與基板的密著性或使液晶配向膜與密封材的密著性提高的密著輔助劑、用於提高液晶配向膜的強度的交聯劑、用於調整液晶配向膜的介電率或電阻的介電質或導電物質等。作為該等追加成分之具體例係如液晶配向劑相關之周知的文獻中所揭示般，若要表示其一例子可舉出公開公報2015/060357號說明書第53頁[0105]~55頁[0116]所揭示的成分等。 [0070] ＜具有液晶配向膜之基板之製造方法＞及＜液晶顯示元件之製造方法＞ 本發明之具有液晶配向膜之基板之製造方法係具有下述步驟： [I] 將含有(A)由二胺成分與酸二酐成分所得之聚合物、及(B)有機溶劑之聚合物組成物塗佈至具有橫向電場驅動用導電膜之基板上後，進行乾燥從而形成塗膜之步驟，該二胺成分由包上述式(1)所表示之二胺，該酸二酐成分包含上述式(2)所表示之四羧酸二酐； [II] 對[I]所得之塗膜照射偏光的紫外線之步驟；及 [III] 將[II]所得之塗膜進行加熱之步驟。 藉由上述步驟，從而可得到被賦予配向控制能之橫向電場驅動型液晶顯示元件用液晶配向膜，並可得到具有該液晶配向膜之基板。 [0071] 又，除了上述所得之基板(第1基板)之外，藉由準備第2基板，從而可得到橫向電場驅動型液晶顯示元件。 第2基板係除了使用不具有橫向電場驅動用導電膜之基板，來替代具有橫向電場驅動用導電膜之基板以外，藉由採用上述步驟[I]~[III](因為使用不具有橫向電場驅動用導電膜之基板，故方便起見，本案中有時也簡稱為步驟[I’]~[III’])，從而可得到具有被賦予配向控制能之液晶配向膜之第2基板。 [0072] 橫向電場驅動型液晶顯示元件之製造方法係具有下述步驟： [IV] 使第1及第2基板的液晶配向膜介隔著液晶並相對之方式來對向配置上述所得之第1及第2基板，從而得到液晶顯示元件之步驟。據此，可得到橫向電場驅動型液晶顯示元件。 [0073] 以下，對於本發明之製造方法所具有之[I]~[III]、及[IV]的各步驟來進行說明。 ＜步驟[I]＞ 步驟[I]中，在具有橫向電場驅動用導電膜之基板上塗佈含有感光性主鏈型高分子及有機溶劑之聚合物組成物後，進行乾燥來形成塗膜。 [0074] ＜基板＞ 關於基板並無特別限定，若所製造的液晶顯示元件為透射型之情形時，以使用透明性高的基板為較佳。此情形時，無特別限定可使用玻璃基板、或丙烯酸基板或聚碳酸酯基板等的塑膠基板等。 又，考慮適用於反射型液晶顯示元件，亦可使用矽晶圓等的不透明的基板。 [0075] ＜橫向電場驅動用導電膜＞ 基板係具有橫向電場驅動用導電膜。 作為該導電膜，若液晶顯示元件為透射型之情形時，可舉出ITO(Indium Tin Oxide：氧化銦錫)、IZO(Indium Zinc Oxide：氧化銦鋅)等，但並非被限定於該等。 又，若為反射型液晶顯示元件之情形時，作為導電膜可舉出鋁等的反射光之材料等，但並非被限定於該等。 在基板上形成導電膜之方法係可使用以往周知的手法。 [0076] 將上述之聚合物組成物塗佈至具有橫向電場驅動用導電膜之基板上之方法並無特別限定。 塗佈方法係以工業上而言採用網板印刷、平板印刷、柔版印刷或噴墨法等來進行之方法為一般的。作為其他的塗佈方法係有浸漬法、輥塗佈機法、縫塗佈機法、旋轉器法(旋轉塗佈法)或噴霧法等，可因應目的來使用該等。 [0077] 在具有橫向電場驅動用導電膜之基板上塗佈聚合物組成物後，可藉由加熱板、熱循環型烘箱或IR(紅外線)型烘箱等的加熱手段，以30~150℃，較佳為70~110℃下使溶劑蒸發從而得到塗膜。若乾燥溫度過低時，溶劑的乾燥將會有變得不足之傾向；又若加熱溫度過高時，則會進行熱醯亞胺化，其結果，因偏光曝光而光分解反應將會過量地進行，此情形時，難以藉由自我組織化而朝單一方向進行再配向，故將會損及配向穩定性。因此，就液晶配向穩定性之觀點而言，此時的乾燥溫度係以特定聚合物實質上未進行熱醯亞胺化的溫度為較佳。 塗膜的厚度過厚時，則在液晶顯示元件的消耗電力方面不利，若過薄時，則有時液晶顯示元件的可靠性將會降低，故較佳為5nm~300nm，又較佳為10nm~150nm。 尚，亦可於[I]步驟之後，接下來的[II]步驟之前，設置將形成有塗膜之基板冷卻至室溫之步驟。 [0078] ＜步驟[II]＞ 於步驟[II]中，對步驟[I]所得之塗膜照射偏光的紫外線。對塗膜的膜面照射偏光的紫外線之情形時，從相對於基板為一定的方向介隔著偏光板來照射經偏光的紫外線。作為使用的紫外線係可使用在波長100nm~400nm的範圍內的紫外線。較佳為依據使用的塗膜的種類，介隔著過濾器等來選擇最佳的波長。又，例如為能夠選擇性的誘發光分解反應，可選擇波長240nm~400nm的範圍內的紫外線來使用。作為紫外線可使用例如從高壓水銀燈或金屬鹵素燈所放射的光。 [0079] 偏光的紫外線的照射量係取決於使用的塗膜。照射量係以設為可實現∆A的最大值(以下亦稱為∆Amax)之偏光紫外線的量的1%~70%的範圍內為較佳，以設為1%~50%的範圍內為又較佳，所述∆A係該塗膜中與偏光紫外線之偏光方向為平行方向之紫外線吸光度、和垂直方向之紫外線吸光度之差。 [0080] ＜步驟[III]＞ 於步驟[III]中，對步驟[II]中照射了偏光的紫外線之塗膜進行加熱。藉由加熱，可賦予塗膜配向控制能。 加熱係可使用加熱板、熱循環型烘箱或IR(紅外線)型烘箱等的加熱手段。加熱溫度係可考慮使用的塗膜所展現出良好的液晶配向穩定性及電特性的溫度來做決定。 [0081] 加熱溫度係以在主鏈型高分子展現出良好的液晶配向穩定性的溫度範圍內為較佳。若加熱溫度過低時，則因為熱所致之異向性的增大效果或熱醯亞胺化將會變得不足之傾向，又若加熱溫度高於溫度範圍時，藉由偏光曝光而被賦予的異向性將會有消失之傾向，此情形時，藉由自我組織化而在一方向上進行再配向會變得困難。 [0082] 加熱後所形成的塗膜的厚度，由於與步驟[I]中所記載之相同理由，故較佳為5nm~300nm，又較佳以50nm~150nm為宜。 [0083] 藉由具有以上之步驟，依據本發明之製造方法能夠實現高效率的對塗膜的異向性的導入。又，可高效率地製造附有液晶配向膜之基板。 [0084] ＜步驟[IV]＞ [IV]步驟係如以下：將[III]所得之在橫向電場驅動用導電膜上具有液晶配向膜之基板(第1基板)、與相同地在上述[I’]~[III’]中所得之不具有導電膜之附有液晶配向膜之基板(第2基板)，介隔著液晶並以雙方的液晶配向膜相對之方式來進行對向配置，並藉由周知的方法製作液晶晶胞，從而製作橫向電場驅動型液晶顯示元件之步驟。尚，步驟[I’]~[III’]，除了在步驟[I]中使用不具有該橫向電場驅動用導電膜之基板，來替代具有橫向電場驅動用導電膜之基板以外，可與步驟[I]~[III]相同地來進行。步驟[I]~[III]與步驟[I’]~[III’]之不同點僅在於有無上述之導電膜，因此省略步驟[I’]~[III’]的說明。 [0085] 若要舉出液晶晶胞或液晶顯示元件之製作之一例子時，可示例下述方法：準備上述之第1及第2基板，在一片的基板的液晶配向膜上散布間隔件，以液晶配向膜面成為內側之方式來貼合另一片基板，減壓注入液晶並密封之方法，或是在散布間隔件的液晶配向膜面上滴加液晶後，將基板貼合並進行密封之方法等。此時，一側的基板係以使用具有如橫向電場驅動用的梳齒般的構造的電極之基板為較佳。此時的間隔件的直徑，係較佳為1μm~30μm，又較佳為2μm~10μm。該間隔件直徑決定挾持液晶層的一對基板間距離，即液晶層的厚度。 [0086] 本發明之附有塗膜之基板之製造方法係將聚合物組成物塗佈至基板上形成塗膜後，照射偏光的紫外線。接下來藉由進行加熱，實現對主鏈型高分子膜的高效率的異向性的導入，製造具備液晶的配向控制能之附有液晶配向膜之基板。 本發明中使用的塗膜中，利用藉由基於主鏈的光反應之自我組織化而誘發之分子再配向之原理，來實現對塗膜的高效率的異向性的導入。本發明之製造方法中，若在主鏈型高分子中具有光分解性基來作為光反應性基的構造之情形時，使用主鏈型高分子在基板上形成塗膜後，照射偏光的紫外線，接下來進行加熱後，製成液晶顯示元件。 [0087] 因此，本發明之方法中使用的塗膜，係藉由依序進行對塗膜照射偏光的紫外線與加熱處理，從而高效率地導入異向性，故可製成配向控制能為優異的液晶配向膜。 [0088] 又，本發明之方法中使用的塗膜中，將對塗膜照射之偏光的紫外線的照射量、與加熱處理中之加熱溫度進行最佳化。藉此，可實現高效率的對塗膜的異向性的導入。 [0089] 對本發明中所使用的塗膜以高效率導入異向性，作為最佳的偏光紫外線的照射量，係對應於該塗膜中感光性基產生光分解反應的量達到最佳時的偏光紫外線的照射量。若對本發明中所使用的塗膜照射偏光的紫外線之結果是進行光分解反應的感光性基少時，則達不到充分的光反應量。此情形時，之後即使加熱亦不會進行充分的自我組織化。 [0090] 因此，本發明中所使用的塗膜中，藉由偏光紫外線的照射而使感光性基進行光分解反應的最佳量，係以該高分子膜設為0.1莫耳%~90莫耳%為較佳，以0.1莫耳% ~80莫耳%為又較佳。藉由使進行光反應的感光性基的量設為如此般的範圍內，藉由之後的加熱處理，自我組織化將可效率佳地進行，將能高效率的在膜中形成異向性。 [0091] 本發明之方法中使用的塗膜中，藉由偏光的紫外線的照射量之最佳化，可將高分子膜的主鏈中之感光性基的光分解反應的量予以最佳化。又，合併之後的加熱處理，可實現高效率的、對本發明中所使用的塗膜的異向性的導入。此情形時，關於適合的偏光紫外線的量，可以基於本發明中所使用的塗膜的紫外吸收的評估來進行。 [0092] 即，對於本發明中所使用的塗膜，分別測定偏光紫外線照射後的與偏光的紫外線之偏光方向為平行方向之紫外線吸收，和垂直方向之紫外線吸收。從紫外吸收之測定結果，評估該塗膜中與偏光的紫外線之偏光方向為平行方向之紫外線吸光度、和垂直方向之紫外線吸光度之差(∆A)。又，求出本發明中所使用的塗膜中所實現的∆A的最大值(∆Amax)，與實現該最大值的偏光紫外線的照射量。本發明之製造方法中，將實現該∆Amax的偏光紫外線照射量作為基準，可決定液晶配向膜的製造中所照射的偏光的紫外線量的較佳量。 [0093] 根據以上，本發明之製造方法中，為了實現對塗膜的高效率的異向性的導入，將該主鏈型高分子可賦予液晶配向穩定性的溫度範圍作為基準，來決定如上述般的適合的加熱溫度。因此，例如，本發明中所使用的主鏈型高分子為賦予液晶配向穩定性的溫度範圍，係可考慮使用的塗膜所展現出良好的液晶配向穩定性及電特性的溫度來做決定，可依據由以往的聚醯亞胺等所成之液晶配向膜的溫度範圍來做設定。即，偏光紫外線照射後的加熱溫度係以設為150℃~300℃為較佳，更希望設為180℃~250℃。藉此，本發明中所使用的塗膜中，將可賦予更大的異向性。 [0094] 藉此，由本發明所提供的液晶顯示元件對於光或熱等的外部應力將展現出高的可靠性。 [0095] 如以上般之方式，使用本發明之聚合物所製造的橫向電場驅動型液晶顯示元件用基板或具有該基板的橫向電場驅動型液晶顯示元件，由於可靠性為優異，故可適合利用於大畫面且高精細的液晶電視等。又，藉由本發明之方法所製造的液晶配向膜，由於具有優異的液晶配向穩定性與可靠性，故亦可利用於使用液晶的可變相移器，該可變相移器係可適合利用於例如能改變共振周波數的天線等。 [實施例] [0096] 實施例中使用的簡稱係如以下般。 NMP：N-甲基-2-吡咯啶酮 BCS：丁基溶纖劑 DA-1：下述構造式(DA-1) DA-2：下述構造式(DA-2) DA-3：下述構造式(DA-3) DA-4：下述構造式(DA-4) DA-5：下述構造式(DA-5) DA-6：下述構造式(DA-6) DA-7：下述構造式(DA-7) DA-8：下述構造式(DA-8) DA-9：下述構造式(DA-9) DA-10：下述構造式(DA-10) CA-1：下述構造式(CA-1) [0097][0098][0099] ＜黏度之測定＞ 合成例中，聚合物溶液的黏度係使用E型黏度計TVE-22H (東機產業公司製)，以樣品量1.1mL、錐形轉子TE-1(1°34’、R24)、溫度25℃下來進行測定。 [0100] (合成例1) 於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取2.93g(12.0mmol)DA-1，加入32.3gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加2.22g(11.3mmol)CA-1，進而加入13.8gNMP，在氮環境下以23℃攪拌8小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係130mPa·s。 將該聚醯胺酸的溶液分離14.5g至已放入攪拌子的100mL三角燒瓶中，加入5.8gNMP、及8.7gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(A-1)。 [0101] (合成例2) 於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取4.30g(15.0mmol)DA-2、加入40.6gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加2.79g(14.3mmol)CA-1，進而加入10.1gNMP，在氮環境下以23℃攪拌5小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係322mPa·s。 將該聚醯胺酸的溶液分離14.9g至已放入攪拌子的100mL三角燒瓶中，加入10.2gNMP、及10.7gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(A-2)。 [0102] (合成例3) 於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取3.60g(12.0mmol)DA-3，加入33.4gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加2.22g(11.3mmol)CA-1，進而加入8.35gNMP，在氮環境下以23℃攪拌3小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係370mPa·s。 將該聚醯胺酸的溶液分離14.5g至已放入攪拌子的100mL三角燒瓶中，加入9.90gNMP、及10.4gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(A-3)。 [0103] (合成例4) 於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取4.11g(12.0mmol)DA-4，加入36.4gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加2.19g(11.2mmol)CA-1，進而加入9.10gNMP，在氮環境下以23℃攪拌5小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係349mPa·s。 將該聚醯胺酸的溶液分離14.6g至已放入攪拌子的100mL三角燒瓶中，加入9.90gNMP、及10.5gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(A-4)。 [0104] (合成例5) 於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取4.17g(13.0mmol)DA-5，加入38.2gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加2.36g(12.0mmol)CA-1，進而加入9.55gNMP，在氮環境下以23℃攪拌6小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係247mPa·s。 將該聚醯胺酸的溶液分離14.7g至已放入攪拌子的100mL三角燒瓶中，加入9.98gNMP、及10.6gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(A-5)。 [0105] (合成例6) 於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取2.49g(23.0mmol)DA-6，加入37.9gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加4.33g(22.1mmol)CA-1，進而加入9.47gNMP，在環境下以23℃攪拌4小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係321mPa·s。 將該聚醯胺酸的溶液分離14.6g至已放入攪拌子的100mL三角燒瓶中，加入9.94gNMP、及10.5gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(A-6)。 [0106] (比較合成例1) 於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取3.45g(15.0mmol)DA-7，加入35.6gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加2.82g(14.4mmol)CA-1，進而加入8.91gNMP，在氮環境下以23℃攪拌20小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係277mPa·s。 將該聚醯胺酸的溶液分離14.9g至已放入攪拌子的100mL三角燒瓶中，加入10.2gNMP、及10.7gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(B-1)。 [0107] (比較合成例2) 於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取3.57g(18.0mmol)DA-8，加入39.4g NMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加3.46g(17.6mmol)CA-1，進而加入9.84gNMP，在環境下以23℃攪拌4小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係218mPa·s。 將該聚醯胺酸的溶液分離14.6g至已放入攪拌子的100mL三角燒瓶中，加入9.94gNMP、及10.5gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(B-2)。 [0108] (比較合成例3) 於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取2.59g(19.0mmol)DA-9，加入35.3gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加3.54g(18.1mmol)CA-1，進而加入8.82gNMP，在氮環境下以23℃攪拌20小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係336mPa·s。 將該聚醯胺酸的溶液分離14.8g至已放入攪拌子的100mL三角燒瓶中，加入10.0g NMP、及10.7g BCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(B-3)。 [0109] (比較合成例4) 於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取2.70g(25.0mmol)DA-10，加入34.0gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加4.80g(24.5mmol)CA-1，進而加入8.51gNMP，在氮環境下以23℃攪拌8小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係301mPa·s。 將該聚醯胺酸的溶液分離12.0g至已放入攪拌子的100mL三角燒瓶中，加入13.2gNMP、及10.8g BCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(B-4)。 [0110] ＜液晶配向性評估用液晶晶胞之製作＞ 以下表示用於評估液晶配向性之液晶晶胞之製作方法。 製作具備FFS方式之液晶顯示元件之構成的液晶晶胞。首先，準備附有電極的基板。基板為30mm×35mm的大小、厚度為0.7mm的玻璃基板。於基板上作為第1層全面地形成構成對向電極的IZO電極。於第1層的對向電極之上，作為第2層形成了藉由CVD法而成膜的SiN(氮化矽)膜。第2層的SiN膜的膜厚為500nm，作為層間絕緣膜發揮作用。於第2層的SiN膜之上，作為第3層配置了將IZO膜圖型化而形成的梳齒狀的像素電極，以形成了第1像素及第2像素這2個像素。各像素的尺寸為長10mm、寬約5mm。此時，第1層的對向電極與第3層的像素電極係藉由第2層的SiN膜的作用而為電絕緣。 第3層的像素電極與特開2014-77845(日本國公開專利公報)所記載的圖相同，具有排列多個中央部分彎曲的“く”字形狀的電極要素所構成的梳齒狀的形狀。各電極要素的寬度方向的寬為3μm，電極要素間的間隔為6μm。形成各像素的像素電極由排列多個中央部分彎曲的“く”字形狀的電極要素所構成，因此各像素的形狀不是長方形，而是具備與電極要素相同地在中央部分彎曲的、與粗體的“く”字相似的形狀。而且，各像素係以其中央的彎曲部分為界被上下分割，具有彎曲部分的上側的第1區域與下側的第2區域。 若比較各像素的第1區域與第2區域時，則構成此等的像素電極的電極要素的形成方向為不同。即，將對基板投影後述之偏光紫外線的偏光面之線段的方向作為基準時，像素的第1區域中，像素電極的電極要素以成為+10°的角度(順時針轉)之方式形成，像素的第2區域中，像素電極的電極要素以成為-10°的角度(順時針轉)之方式形成。即，各像素的第1區域與第2區域中，以藉由像素電極與對向電極之間的電壓外加而所誘發的液晶的、在基板面內的旋轉動作(面內轉向)的方向互為相反方向之方式來構成。 [0111] 接下來，利用1.0μm的過濾器來過濾合成例及比較合成例所得之液晶配向劑後，藉由旋轉塗佈來塗佈至所準備的上述附有電極的基板上。接下來，於設定成70℃的加熱板上使其乾燥90秒鐘。接下來，利用Ushio電機(股)製曝光裝置：APL-L050121S1S-APW01，介隔著波長選擇過濾器及偏光板，從鉛垂方向對基板來照射紫外線的直線偏光。此時，對基板投影的偏光紫外線的偏光面之線段的方向，係以相對於第3層IZO梳齒電極成為傾斜10°的方向之方式來設定偏光面方向。接下來，利用設定成230℃的IR(紅外線)型烘箱進行30分鐘燒成，從而得到施予配向處理的膜厚100nm之附有聚醯亞胺液晶配向膜的基板。又，作為對向基板，對於在裏面形成有ITO電極的具有高度4μm的柱狀間隔件的玻璃基板，亦與上述相同之方式，從而得到施予配向處理的附有聚醯亞胺液晶配向膜的基板。將該等2片附有液晶配向膜的基板作為1組，於一片的基板上以保留液晶注入口之形式下印刷密封劑，將另1片基板以液晶配向膜面彼此相對、且對基板投影偏光紫外線的偏光面之線段的方向成平行之方式來貼合並壓黏。之後，使密封劑硬化從而製作晶胞間距為4μm的空晶胞。藉由減壓注入法對該空晶胞注入液晶MLC-7026-100(Merck公司製負型液晶)，並密封注入口從而得到FFS方式之液晶晶胞。之後，將所得之液晶晶胞以120℃下加熱30分鐘，以23℃下放置一晩後使用於液晶配向性之評估。 [0112] ＜液晶配向性之評估＞ 使用該液晶晶胞，以70℃的恆溫環境下，外加168小時周波數30Hz下16VPP的交流電壓。之後，使液晶晶胞的像素電極與對向電極之間成為短路狀態，保持其狀態以23℃下放置一晩。 放置後，將液晶晶胞設置在以偏光軸為垂直之方式所配置的2片的偏光板之間，在無外加電壓之狀態下點亮背光源，以透射光的輝度達到最小之方式來調整液晶晶胞的配置角度。而且，計算使液晶晶胞從第1像素的第2區域達到最暗的角度旋轉至第1區域達到最暗的角度為止的旋轉角度作為角度∆。針對第2像素亦為相同地，將第2區域與第1區域進行比較並算出相同的角度∆。而且，計算第1像素與第2像素的角度∆值的平均值作為液晶晶胞的角度∆。若該液晶晶胞的角度∆的值未滿1.0°時定義為「良好」，若角度∆的值為1.0°以上時則定義為「不良」來評估。 [0113] (實施例1) 使用合成例1所得之液晶配向劑(A-1)，來製作如上述記載般的液晶晶胞。偏光紫外線的照射係利用高壓水銀燈，介隔著波長選擇過濾器：240LCF、及254nm型的偏光板來進行。偏光紫外線的照射量係藉由利用Ushio電機(股)製照度計UVD-S254SB來測定光量，並在波長254nm下分別變更以600~1500mJ/cm2
的範圍內來實施，從而製作3個以上的偏光紫外線照射量不同的液晶晶胞。 對於該等之液晶晶胞進行評估液晶配向性之結果，角度∆為最佳的偏光紫外線照射量為1200mJ/cm2
，角度∆係以0.13°為良好。 [0114] (實施例2~6) 除了使用合成例2~6所得之液晶配向劑以外，採用與實施例1相同之方法來評估液晶配向性。 [0115] (比較例1~4) 除了使用比較合成例1~4所得之液晶配向劑以外，採用與實施例1相同之方法來評估液晶配向性。 [0116] 表1中表示使用合成例及比較合成例所得之液晶配向劑時，角度∆為最佳的偏光紫外線照射量、及液晶配向性之評估的結果。 [0117][0118] 如表1所表示般，實施例1~6中，交流驅動前後的配向方位角的差(角度∆)未滿1.0°為良好，因此液晶顯示元件之顯示品質提升為優異。另一方面，比較例1~4中，角度∆為1.0°以上而為不良。 如此般地藉由本發明之方法所製造之液晶顯示元件係可確認展現出非常優異的殘影特性。 [產業利用性] [0119] 使用本發明之組成物所製造的橫向電場驅動型液晶顯示元件用基板或具有該基板的橫向電場驅動型液晶顯示元件，由於液晶配向的長期穩定性為優異，故可適合利用於大畫面且高精細的液晶電視等。又，藉由本發明之方法所製造的液晶配向膜係亦可利用於使用液晶的可變相移器，該可變相移器係可適合利用於例如能改變共振周波數的天線等。[Best Mode for Carrying Out the Invention] [0024] Hereinafter, embodiments of the present invention will be described in detail. The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent containing a polymer (hereinafter, also referred to as a specific polymer or a main chain polymer) obtained from a diamine component and an acid dianhydride component. The amine component contains a diamine represented by the formula (1), and the acid dianhydride component contains a tetracarboxylic dianhydride represented by the formula (2). Each condition is described in detail below. [Diamine having a specific structure] The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent containing a polymer and an organic solvent. The polymer is obtained from a diamine component and an acid dianhydride component. The diamine component Contains a diamine represented by formula (1) (also referred to as a specific diamine in the present invention), and the acid dianhydride component comprises a tetracarboxylic dianhydride represented by formula (2) (also referred to as a specific tetracarboxylic acid in the present invention) Acid dianhydride). [0026] [0027] In the formula (1), L is a divalent organic group having 2 or more carbon atoms and contains both an alkylene group and a bond selected from the group consisting of an ether bond and an ester bond, R 1 And R 2 Is independently a monovalent organic group, p1 and p2 are each independently an integer of 0 to 4, p is 0 or 1, and q1 and q2 are each independently 1 or 2. [0028] Examples of the monovalent organic group include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, or a fluorine group having a carbon number of 1 to 10 (preferably 1 to 3). Alkoxy. Among them, a methyl group is preferred as the monovalent organic group. [0029] Examples of the divalent organic group include a group composed of an alkylene group and an ether bond, a group composed of an alkylene group and an ester bond, and a part or all of a hydrogen atom substituted with a halogen atom. A group consisting of an alkylene group and an ether bond, or a group consisting of an alkylene group and an ester bond in which a part or all of a hydrogen atom is replaced by a halogen. Among them, a divalent organic group is preferably a group composed of an alkylene group and an ether bond. The carbon number is preferably 2 or more and 20 or less, and more preferably 2 or more and 10 or less. [0030] If the total number of carbon atoms and oxygen atoms related to the length of the main chain among the number of atoms of L is an even number, the linearity of the obtained polymer becomes high, and as a result, In the heating step after polarized light irradiation, it is preferable to perform re-alignment in a higher order to obtain a liquid crystal alignment film that imparts high alignment control ability. The total number of carbon atoms and oxygen atoms related to the length of the main chain means that the number of each methylene group in the main chain is set to 1, the number of each ether bond is set to 1, and The total number of one ester bond is set to two. [0031] As p1 and p2, 0 is preferable in terms of less steric hindrance, phenyl groups easily overlap each other, and realignment in a higher order. As p, 1 is preferable in that an alkylene group having a function as a free rotation part can be realigned in a higher order. Among the diamines of the formula (1), specific examples of the diamines in which p is 1 can be exemplified as follows, but are not limited thereto. [0032] [0033] [0034] [0035] Here, if the total of r, t, and u is an even number such as 2, 4, 6, 8, and 10, the linearity of the obtained polymer will be high. As a result, after polarized light irradiation, In the heating step, by performing re-alignment in a higher order, a liquid crystal alignment film having high alignment control ability can be obtained. s is an odd number of 1, 3, 5, etc., but it is preferable for the reasons described above. Among the diamines represented by the formula (1), as a specific example of the diamine having p of 0, p-phenylenediamine is mentioned. [Polymer] The polymer of the present invention is a polymer obtained from a diamine component and an acid dianhydride component, and the diamine component includes the diamine represented by the above formula (1), and the acid dianhydride component It contains the tetracarboxylic dianhydride represented by the said Formula (2). Specific examples include polyamic acid, polyamidate, polyimide, polyurea, polyamidine, and the like. From the viewpoint of use as a liquid crystal alignment agent, it is selected from the group consisting of the following formula: (3) At least one of the polyimide precursor of the structural unit represented by the structural unit and the polyimide of the amidoimide is preferable. In the heating step after polarized light irradiation, in terms of the more freely rotating parts in the polymer, realignment can be performed in a higher order, a polyfluorene imide precursor is more preferred. [0037] [0038] In the above formula (3), X 1 Is a tetravalent organic group derived from the tetracarboxylic acid derivative represented by the above formula (2), Y 1 Is a divalent organic group derived from a diamine containing a structure of formula (1), R 11 It is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. From the point of being easily imidized by heating, R 11 A hydrogen atom, a methyl group or an ethyl group is preferred, and a hydrogen atom is more preferred. <Tetracarboxylic dianhydride> X 1 It is a tetravalent organic group derived from the tetracarboxylic acid derivative represented by the said Formula (2). In formula (2), R 6 ~ R 9 In the following structures, each is independently a hydrogen atom, an alkyl group, a halogen atom, or a phenyl group. From the viewpoint of liquid crystal alignment, R is 6 ~ R 9 It is preferably a hydrogen atom. [0040] <Diamine> In the formula (3), Y is 1 Specific examples include a structure obtained by removing two amine groups from the diamine of the formula (1). Among them, a structure in which two amine groups are removed from the above-mentioned preferred diamine is preferable. [0042] <Polymer (other structural unit)> The polyimide precursor containing the structural unit represented by formula (3) may also be selected from the following as long as the effect of the present invention is not impaired. At least one of a structural unit represented by formula (4) and a polyfluorene imine of the sulfonium imide. [0043] [0044] In the formula (4), X 2 Is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y 2 Is a divalent organic radical derived from a diamine, R 12 Is the same as R in the aforementioned formula (3) 11 Is defined the same, R twenty two Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Again, 2 R twenty two At least one of them is preferably a hydrogen atom. X 2 It is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. X in the polyimide precursor 2 It is appropriately selected in accordance with the degree of characteristics required for the solubility of the polymer in the solvent or the coating property of the liquid crystal alignment agent, the alignment property of the liquid crystal when the liquid crystal alignment film is made, the voltage retention rate, and the stored charge. One type of polymer may be present, or two or more types may be mixed. [0045] To represent X 2 As a specific example, the structures of the formulae (X-1) to (X-46) listed on pages 13 to 14 of International Publication Gazette 2015/119168 can be cited. Although the following represents a better X 2 Structure, but the present invention is not limited to these. [0046] [0047] [0048] Y in the polyimide precursor 2 It is a divalent organic group derived from a diamine, and its structure is not particularly limited. Also, Y 2 It is appropriately selected in accordance with the degree of characteristics required for the solubility of the polymer in the solvent or the coating property of the liquid crystal alignment agent, the alignment property of the liquid crystal when the liquid crystal alignment film is made, the voltage retention rate, and the stored charge. One type of polymer may be present, or two or more types may be mixed. [0049] To represent Y 2 Specific examples include the structure of formula (2) on page 4 of International Publication Gazette 2015/119168, and the formulas (Y-1) to (Y-97) on pages 8 to 12, Structures of (Y-101) ~ (Y-118); Divalent organic group formed by removing two amine groups in formula (2), published on page 6 of International Publication Gazette 2013/008906; International Publication Gazette 2015 / A bivalent organic group obtained by removing two amine groups in formula (1), as shown in page 8 of 122413; a structure of formula (3), which is shown in page 8 of International Publication Gazette 2015/060360; published in Japan A bivalent organic group obtained by removing two amine groups from formula (1) as listed on page 8 of Patent Bulletin 2012-173514; and represented by formula (A) ~ (published on page 9 of International Publication 2010-050523) F) A divalent organic group or the like obtained by removing two amine groups. [0050] As Preferred Y 2 As a structure, the structure of following formula (5) is mentioned. Shang, Y 2 The structure may be a structure derived from a specific diamine (1). [0051] [0052] In the formula (5), R 32 It is a single bond or a divalent organic group, and a single bond is preferred. R 33 Department- (CH 2 ) n -The indicated structure. n is an integer from 2 to 10, and 3 to 7 is preferred. Also, any -CH 2 -Under the condition that they are not adjacent, they can be replaced by ether, ester, amidine, urea, and carbamate bonds. R 34 It is a single bond or a divalent organic group. Any hydrogen atom system on the benzene ring may be substituted by a monovalent organic group, and a fluorine atom or a methyl group is preferred. Specific examples of the structure represented by the formula (5) include the following structures, but the invention is not limited to these structures. [0053] [0054] [0055] [0056] [0057] [0058] Among them, the point that does not hinder the reorientation of at least one selected from the group consisting of a polyimide precursor containing a structural unit represented by formula (3) and a polyimide of the amidoimide It is preferable to include a structure common to the specific diamine (1). [0059] If the polyimide precursor containing the structural unit represented by formula (3) also includes the structural unit represented by formula (4), the structural unit represented by formula (3) is relative to the formula ( 3) The total with formula (4) is preferably 30 mol% to 100 mol%, more preferably 50 mol% to 100 mol%, and particularly preferably 70 mol% to 100 mol%. [0060] The molecular weight of the polyimide precursor used in the present invention is preferably a weight average molecular weight of 2,000 to 500,000, more preferably 5,000 to 300,000, more preferably 10,000 to 100,000. Examples of the polyimide used in the present invention include a polyimide obtained by closing the aforementioned polyimide precursor. In this polyfluorene imine, the ring closure ratio (also referred to as the fluorene imidization ratio) of the amidino group does not necessarily need to be 100%, and can be arbitrarily adjusted according to the use or purpose. Regarding the polymer of the present invention, from the viewpoint of liquid crystal alignment, the imidization ratio is preferably from 0 to 70%, and more preferably from 0 to 50%. Examples of the method for polyimide precursor imidization include hot imidization by directly heating a solution of the polyimide precursor, or adding a catalyst to the solution of the polyimide precursor. The catalyst is imidization. [0061] <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains a polymer (specific polymer) obtained from a diamine component and an acid dianhydride component, and the diamine component contains the diamine represented by the above formula (1) Although this acid dianhydride component contains the tetracarboxylic dianhydride represented by the said Formula (2), as long as the effect described by this invention can be exhibited, it may contain the specific polymer of 2 or more different structures. In addition to the specific polymer, other polymers, that is, polymers which do not have a divalent group derived from a diamine represented by formula (1), may be contained. Examples of other types of polymers include polyamic acid, polyimide, polyamidate, polyester, polyamine, polyurea, polyorganosiloxane, cellulose derivative, and polycondensation. Aldehydes, polystyrene or derivatives thereof, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like. When the liquid crystal alignment agent of the present invention contains other polymers, the ratio of the specific polymer to the total polymer component is preferably 10% by mass or more. As an example, it may be 10 to 100% by mass. %. [0062] A liquid crystal alignment agent is used for producing a liquid crystal alignment film. From the viewpoint of forming a uniform thin film, it is generally in the form of a coating liquid. Even the liquid crystal alignment agent of the present invention is preferably a coating liquid containing the aforementioned polymer component and an organic solvent that dissolves the polymer component. At this time, the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed according to the thickness setting of the coating film to be formed. In terms of forming a uniform and non-defective coating film, 1% by mass or more is preferable, and in terms of storage stability of the solution, 10% by mass or less is preferable. The concentration of the particularly good polymer is 2 to 8% by mass. [0063] The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as it can uniformly dissolve the polymer component. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2 -Pyrrolidone, dimethyl sulfenyl, γ-butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and the like. Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone. [0064] In addition to the solvents described above, the organic solvent contained in the liquid crystal alignment agent may generally be used in combination with a solvent that improves the coatability when applying the liquid crystal alignment agent or the surface smoothness of the coating film. Even if it is the liquid crystal alignment agent of the present invention, such a mixed solvent can be suitably used. Specific examples of the organic solvent used in combination are listed below, but they are not limited to these examples. [0065] Examples include ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, and 2-methyl alcohol. 1-butanol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- 2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, Cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol , 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Alcohol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethyl Glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl ethyl Acid ester, 1-methylpentyl acetate, 2 -Ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethyl acetate, 2- (methoxy (Methoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol mono Butyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, Tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol Alcohol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethyl Glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate , Propylene glycol monoethyl ether, methyl pyruvate, pyruvate Ester, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, Propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, the following formula [D -1] ~ [D-3], etc. [0066] In the formula [D-1], D 1 Is an alkyl group having 1 to 3 carbon atoms. In the formula [D-2], D 2 Is an alkyl group having 1 to 3 carbon atoms. In the formula [D-3], D 3 Represents an alkyl group having 1 to 4 carbon atoms. [0068] The type and content of such solvents can be appropriately selected according to the coating device, coating conditions, coating environment, and the like of the liquid crystal alignment agent. [0069] The liquid crystal alignment agent of the present invention may further contain components other than the polymer component and the organic solvent, as long as the effect of the present invention is not impaired. Examples of such additional components include adhesion promoters for improving the adhesion between the liquid crystal alignment film and the substrate, or adhesion between the liquid crystal alignment film and the sealing material, and for improving the strength of the liquid crystal alignment film. Cross-linking agents, dielectric materials or conductive materials for adjusting the permittivity or resistance of the liquid crystal alignment film. Specific examples of these additional components are as disclosed in well-known documents related to liquid crystal alignment agents. To show an example, the publication can be found in the publication No. 2015/060357, page 53 [0105] to page 55 [0116] ] Revealed ingredients, etc. [0070] <Manufacturing Method of Substrate with Liquid Crystal Alignment Film> and <Manufacturing Method of Liquid Crystal Display Element> The method for manufacturing a substrate with a liquid crystal alignment film according to the present invention has the following steps: [I] containing (A) by A step of forming a coating film by coating a polymer obtained from a diamine component and an acid dianhydride component and a polymer composition of (B) an organic solvent on a substrate having a conductive film for driving a transverse electric field, and then drying the coating film. The amine component is composed of a diamine represented by the above formula (1), and the acid dianhydride component includes a tetracarboxylic dianhydride represented by the above formula (2); [II] irradiating polarized ultraviolet rays to the coating film obtained in [I] Step; and [III] a step of heating the coating film obtained in [II]. Through the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is provided can be obtained, and a substrate having the liquid crystal alignment film can be obtained. [0071] In addition to the substrate (first substrate) obtained as described above, by preparing a second substrate, a lateral electric field drive type liquid crystal display element can be obtained. The second substrate is a substrate without a conductive film for lateral electric field driving, instead of a substrate with a conductive film for lateral electric field driving, by adopting the above steps [I] to [III] (because the driving without lateral electric field is used) A substrate of a conductive film is used, so for convenience, this case may also be simply referred to as steps [I '] to [III']), so that a second substrate having a liquid crystal alignment film provided with an alignment control ability can be obtained. [0072] A method for manufacturing a lateral electric field-driven liquid crystal display element has the following steps: [IV] The first liquid crystal alignment films of the first and second substrates are arranged opposite to each other with a liquid crystal interposed therebetween, and the first obtained And a second substrate to obtain a liquid crystal display element. According to this, a lateral electric field drive type liquid crystal display element can be obtained. [0073] Hereinafter, each step of [I] to [III] and [IV] included in the manufacturing method of the present invention will be described. <Step [I]> In step [I], a polymer composition containing a photosensitive main chain polymer and an organic solvent is coated on a substrate having a conductive film for lateral electric field drive, and then dried to form a coating film. [Substrate] The substrate is not particularly limited, and if the manufactured liquid crystal display element is of a transmissive type, it is preferable to use a substrate with high transparency. In this case, a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or the like can be used without particular limitation. Further, it is considered to be applicable to a reflective liquid crystal display element, and an opaque substrate such as a silicon wafer may be used. [0075] <Conductive Film for Transverse Electric Field Drive> The substrate includes a conductive film for lateral electric field drive. As the conductive film, in the case where the liquid crystal display element is a transmissive type, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and the like are mentioned, but it is not limited to these. In the case of a reflective liquid crystal display element, a material for reflecting light such as aluminum may be mentioned as the conductive film, but it is not limited thereto. As a method for forming a conductive film on a substrate, a conventionally known method can be used. [0076] The method of applying the above-mentioned polymer composition to a substrate having a conductive film for lateral electric field driving is not particularly limited. The coating method is generally carried out industrially by a screen printing method, a lithographic printing method, a flexographic printing method, or an inkjet method. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (spin coating method), or a spray method, and these can be used depending on the purpose. [0077] After coating the polymer composition on a substrate having a conductive film for lateral electric field drive, it can be heated at 30 to 150 ° C by heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven. The solvent is preferably evaporated at 70 to 110 ° C to obtain a coating film. If the drying temperature is too low, the drying of the solvent tends to become insufficient; and if the heating temperature is too high, the thermal imidization will proceed. As a result, the photodecomposition reaction due to polarized light exposure will be excessive. In this case, it is difficult to re-align in a single direction by self-organization, so the alignment stability will be impaired. Therefore, from the viewpoint of liquid crystal alignment stability, the drying temperature at this time is preferably a temperature at which the specific polymer is not substantially thermally imidized. When the thickness of the coating film is too thick, the power consumption of the liquid crystal display element is disadvantageous. When the thickness of the coating film is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, it is preferably 5 nm to 300 nm, and more preferably 10 nm. ~ 150nm. Alternatively, after the step [I] and before the next step [II], a step of cooling the substrate on which the coating film is formed to room temperature may be provided. [Step [II]> In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When the film surface of the coating film is irradiated with polarized ultraviolet rays, the polarized ultraviolet rays are irradiated through a polarizing plate with a certain direction from the substrate. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. It is preferable to select an optimal wavelength depending on the type of the coating film to be used, with a filter or the like interposed therebetween. Further, for example, in order to selectively induce a photodecomposition reaction, ultraviolet rays having a wavelength in a range of 240 nm to 400 nm can be selected and used. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp or a metal halide lamp can be used. [0079] The irradiation amount of polarized ultraviolet rays depends on the coating film used. The exposure amount is preferably in the range of 1% to 70% of the amount of polarized ultraviolet rays that can achieve the maximum value of ΔA (hereinafter also referred to as ΔAmax), and is set in the range of 1% to 50%. To be more preferable, the ΔA is the difference between the ultraviolet absorbance of the coating film parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance of the vertical direction. [0080] <Step [III]> In step [III], the coating film irradiated with polarized ultraviolet rays in step [II] is heated. By heating, an alignment control ability can be provided to a coating film. As the heating system, heating means such as a hot plate, a thermal cycle type oven, or an IR (infrared) type oven can be used. The heating temperature may be determined by considering a temperature at which the coating film used exhibits good liquid crystal alignment stability and electrical characteristics. [0081] The heating temperature is preferably within a temperature range in which the main chain polymer exhibits good liquid crystal alignment stability. If the heating temperature is too low, the effect of increasing the anisotropy due to heat or thermal imidization will become insufficient, and if the heating temperature is higher than the temperature range, it will be affected by polarized light exposure. The anisotropy imparted will tend to disappear. In this case, it becomes difficult to reorient in one direction by self-organization. [0082] The thickness of the coating film formed after heating is preferably 5 nm to 300 nm, and more preferably 50 nm to 150 nm, for the same reason as described in step [1]. [0083] By having the above steps, the manufacturing method according to the present invention can achieve an efficient introduction of anisotropy into a coating film. In addition, a substrate with a liquid crystal alignment film can be manufactured efficiently. [0084] <Step [IV] The step [IV] is as follows: the substrate (first substrate) having the liquid crystal alignment film on the conductive film for lateral electric field drive obtained in [III] is the same as in [I] above The substrate (second substrate) with a liquid crystal alignment film without a conductive film obtained in '] ~ [III'] is arranged opposite to each other with the liquid crystal alignment films interposed therebetween, and borrows A step of fabricating a liquid crystal cell by a well-known method to fabricate a lateral electric field driving type liquid crystal display element. Steps [I '] to [III'] can be performed in the same manner as in step [I] except that the substrate without the conductive film for lateral electric field drive is used instead of the substrate with the conductive film for lateral electric field drive in step [I]. I] to [III] are performed in the same manner. Steps [I] to [III] differ from steps [I '] to [III'] only in the presence or absence of the above-mentioned conductive film, so the description of steps [I '] to [III'] is omitted. [0085] To give an example of the production of a liquid crystal cell or a liquid crystal display element, the following method may be exemplified: preparing the above-mentioned first and second substrates, and dispersing a spacer on the liquid crystal alignment film of one substrate A method of bonding another substrate such that the liquid crystal alignment film surface becomes the inner side, injecting the liquid crystal under reduced pressure and sealing, or a method of bonding the substrates and sealing after dropping liquid crystals on the liquid crystal alignment film surface of the spacer. Wait. At this time, the substrate on one side is preferably a substrate using an electrode having a structure like a comb tooth for lateral electric field driving. The diameter of the spacer at this time is preferably 1 μm to 30 μm, and more preferably 2 μm to 10 μm. The diameter of the spacer determines the distance between a pair of substrates holding the liquid crystal layer, that is, the thickness of the liquid crystal layer. [0086] The method for manufacturing a substrate with a coating film of the present invention is to apply a polymer composition to a substrate to form a coating film, and then irradiate polarized ultraviolet rays. Next, by heating, the introduction of a high-efficiency anisotropy into the main-chain type polymer film is performed, and a substrate with a liquid crystal alignment film having an alignment control function for liquid crystals is manufactured. In the coating film used in the present invention, the principle of molecular realignment induced by the self-organization of the photo-response based on the main chain is used to realize the introduction of highly efficient anisotropy into the coating film. In the manufacturing method of the present invention, if the main chain polymer has a photodegradable group as a photoreactive group structure, the main chain polymer is used to form a coating film on a substrate and then irradiate polarized ultraviolet rays. Next, after heating, a liquid crystal display element is produced. [0087] Therefore, the coating film used in the method of the present invention can sequentially introduce anisotropy by sequentially irradiating the coating film with polarized ultraviolet rays and heat treatment, so that it can be made to have excellent alignment control performance. Liquid crystal alignment film. [0088] In the coating film used in the method of the present invention, the irradiation amount of the polarized ultraviolet light irradiated to the coating film and the heating temperature in the heat treatment are optimized. This makes it possible to efficiently introduce anisotropy into the coating film. [0089] The anisotropy is introduced into the coating film used in the present invention with high efficiency, and the optimum irradiation amount of polarized ultraviolet light corresponds to the time when the amount of photodecomposition reaction of the photosensitive group in the coating film reaches the optimum. Exposure to polarized ultraviolet rays. When the coating film used in the present invention is irradiated with polarized ultraviolet rays, when the number of photosensitive groups that undergo photodecomposition reaction is small, a sufficient photoreaction amount cannot be achieved. In this case, sufficient self-organization will not be performed even after heating. [0090] Therefore, in the coating film used in the present invention, the optimum amount of the photodegradation reaction of the photosensitive group by irradiation of polarized ultraviolet light is such that the polymer film is 0.1 mol% to 90 mol. Ear% is better, and 0.1 to 80 mole% is more preferred. By setting the amount of the photosensitive group that performs the photoreaction within such a range, self-organization can be performed efficiently by the subsequent heat treatment, and anisotropy can be formed in the film with high efficiency. [0091] In the coating film used in the method of the present invention, the amount of photodecomposition reaction of the photosensitive groups in the main chain of the polymer film can be optimized by optimizing the irradiation amount of polarized ultraviolet rays. . In addition, the combined heat treatment can achieve efficient introduction of anisotropy into the coating film used in the present invention. In this case, an appropriate amount of polarized ultraviolet rays can be performed based on the evaluation of the ultraviolet absorption of the coating film used in the present invention. [0092] That is, for the coating film used in the present invention, the ultraviolet absorption parallel to the polarization direction of the polarized ultraviolet radiation and the ultraviolet absorption in the vertical direction after the polarized ultraviolet radiation were measured. From the measurement results of the ultraviolet absorption, the difference (ΔA) between the ultraviolet absorbance in the parallel direction and the ultraviolet absorbance in the vertical direction in the coating film and the polarized ultraviolet direction was evaluated. In addition, the maximum value (ΔAmax) of ΔA achieved in the coating film used in the present invention and the irradiation amount of polarized ultraviolet rays to achieve the maximum were obtained. In the manufacturing method of the present invention, based on the amount of polarized ultraviolet radiation to achieve the ΔAmax as a reference, a preferable amount of the amount of polarized ultraviolet radiation to be irradiated in the manufacture of the liquid crystal alignment film can be determined. [0093] Based on the above, in the manufacturing method of the present invention, in order to achieve efficient anisotropy introduction of the coating film, the temperature range in which the main chain polymer can impart liquid crystal alignment stability is used as a reference to determine, for example, Suitable heating temperature as described above. Therefore, for example, the main chain polymer used in the present invention is a temperature range that imparts liquid crystal alignment stability, and can be determined by considering a temperature at which the used coating film exhibits good liquid crystal alignment stability and electrical characteristics. It can be set in accordance with the temperature range of a liquid crystal alignment film made of conventional polyfluorene and the like. That is, the heating temperature after irradiation with polarized ultraviolet light is preferably set to 150 ° C to 300 ° C, and more preferably set to 180 ° C to 250 ° C. Accordingly, the coating film used in the present invention can impart greater anisotropy. [0094] Accordingly, the liquid crystal display element provided by the present invention will exhibit high reliability against external stress such as light or heat. [0095] As described above, the substrate for a lateral electric field drive type liquid crystal display element manufactured using the polymer of the present invention or a lateral electric field drive type liquid crystal display element having the substrate is excellent in reliability, and can be suitably used. For large-screen and high-definition LCD TVs. In addition, the liquid crystal alignment film manufactured by the method of the present invention has excellent liquid crystal alignment stability and reliability, so it can also be used in a variable phase shifter using liquid crystals. The variable phase shifter is suitable for use in, for example, Antennas that can change the number of resonance cycles. [Examples] The abbreviations used in the examples are as follows. NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolvant DA-1: The following structural formula (DA-1) DA-2: The following structural formula (DA-2) DA-3: The following structure Formula (DA-3) DA-4: The following structural formula (DA-4) DA-5: The following structural formula (DA-5) DA-6: The following structural formula (DA-6) DA-7: The following The structural formula (DA-7) DA-8: The following structural formula (DA-8) DA-9: The following structural formula (DA-9) DA-10: The following structural formula (DA-10) CA-1 : The following structural formula (CA-1) [0098] [Measurement of Viscosity] In the synthesis example, the viscosity of the polymer solution was an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a tapered rotor TE-1 (1 ° 34 ', R24), and the temperature was measured at 25 ° C. (Synthesis example 1) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.93 g (12.0 mmol) of DA-1 was measured, 32.3 g of NMP was added, and the mixture was stirred while being fed with nitrogen. Dissolve. While stirring the diamine solution under water cooling, 2.22 g (11.3 mmol) of CA-1 was added, 13.8 g of NMP was further added, and the mixture was stirred at 23 ° C. for 8 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 130 mPa · s. 14.5 g of this polyamic acid solution was separated into a 100 mL conical flask placed in a stirrer, 5.8 g of NMP and 8.7 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (A-1). (Synthesis Example 2) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 4.30 g (15.0 mmol) of DA-2 was measured, 40.6 g of NMP was added, and the mixture was stirred while being fed with nitrogen. Dissolve. While stirring this diamine solution under water cooling, 2.79 g (14.3 mmol) of CA-1 was added, and 10.1 g of NMP was further added, followed by stirring at 23 ° C. for 5 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 322 mPa · s. 14.9 g of this polyamic acid solution was separated into a 100 mL conical flask placed in a stirrer, 10.2 g of NMP and 10.7 g of BCS were added, and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (A-2). (Synthesis Example 3) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 3.60 g (12.0 mmol) of DA-3 was measured, 33.4 g of NMP was added, and the mixture was stirred while being fed with nitrogen. Dissolve. While stirring the diamine solution under water cooling, 2.22 g (11.3 mmol) of CA-1 was added, and 8.35 g of NMP was further added, followed by stirring at 23 ° C. for 3 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 370 mPa · s. Separate 14.5 g of the polyamic acid solution into a 100 mL conical flask placed in a stirrer, add 9.90 g of NMP and 10.4 g of BCS, and stir with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (A-3). (Synthesis Example 4) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 4.11 g (12.0 mmol) of DA-4 was measured, 36.4 g of NMP was added, and the mixture was stirred while being fed with nitrogen. Dissolve. While stirring the diamine solution under water cooling, 2.19 g (11.2 mmol) of CA-1 was added, and then 9.10 g of NMP was added, followed by stirring at 23 ° C. for 5 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 349 mPa · s. 14.6 g of this polyamic acid solution was separated into a 100 mL conical flask placed in a stirrer, 9.90 g of NMP and 10.5 g of BCS were added, and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (A-4). (Synthesis Example 5) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 4.17 g (13.0 mmol) of DA-5 was measured, 38.2 g of NMP was added, and the mixture was stirred while being fed with nitrogen. Dissolve. While stirring this diamine solution under water cooling, 2.36 g (12.0 mmol) of CA-1 was added, and then 9.55 g of NMP was added, followed by stirring at 23 ° C. for 6 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 247 mPa · s. 14.7 g of this polyamic acid solution was separated into a 100 mL conical flask placed in a stirrer, 9.98 g of NMP and 10.6 g of BCS were added, and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (A-5). (Synthesis Example 6) In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.49 g (23.0 mmol) of DA-6 was measured, 37.9 g of NMP was added, and the mixture was stirred while being fed with nitrogen. Dissolve. While stirring this diamine solution under water cooling, 4.33 g (22.1 mmol) of CA-1 was added, and 9.47 g of NMP was further added, followed by stirring at 23 ° C. for 4 hours under an environment to obtain a polyamic acid solution. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 321 mPa · s. 14.6 g of the polyamic acid solution was separated into a 100 mL conical flask placed in a stirrer, 9.94 g of NMP and 10.5 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (A-6). [Comparative Synthesis Example 1] In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 3.45 g (15.0 mmol) of DA-7 was measured, 35.6 g of NMP was added, and stirring was performed while feeding nitrogen. Its dissolved. While stirring this diamine solution under water cooling, 2.82 g (14.4 mmol) of CA-1 was added, and 8.91 g of NMP was further added, followed by stirring at 23 ° C. for 20 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 277 mPa · s. 14.9 g of this polyamic acid solution was separated into a 100 mL conical flask placed in a stirrer, 10.2 g of NMP and 10.7 g of BCS were added, and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (B-1). [Comparative Synthesis Example 2] In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 3.57 g (18.0 mmol) of DA-8 was measured, 39.4 g of NMP was added, and stirring was performed while feeding nitrogen. Let it dissolve. While stirring this diamine solution under water cooling, 3.46 g (17.6 mmol) of CA-1 was added, and then 9.84 g of NMP was added, followed by stirring at 23 ° C. for 4 hours under an environment to obtain a polyamic acid solution. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 218 mPa · s. 14.6 g of this polyamic acid solution was separated into a 100 mL conical flask placed in a stirrer, 9.94 g of NMP and 10.5 g of BCS were added, and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (B-2). [Comparative Synthesis Example 3] In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.59 g (19.0 mmol) of DA-9 was measured, 35.3 g of NMP was added, and nitrogen was added while stirring to make Its dissolved. While stirring this diamine solution under water cooling, 3.54 g (18.1 mmol) of CA-1 was added, and then 8.82 g of NMP was added, followed by stirring at 23 ° C. for 20 hours under a nitrogen atmosphere to obtain a solution of polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 336 mPa · s. Separate 14.8 g of the polyamic acid solution into a 100 mL conical flask placed in a stirrer, add 10.0 g of NMP and 10.7 g of BCS, and stir with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (B-3 ). [Comparative Synthesis Example 4] In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.70 g (25.0 mmol) of DA-10 was measured, 34.0 g of NMP was added, and stirring was performed while feeding nitrogen. Its dissolved. While stirring the diamine solution under water cooling, 4.80 g (24.5 mmol) of CA-1 was added, and 8.51 g of NMP was further added, followed by stirring at 23 ° C. for 8 hours under a nitrogen environment to obtain a solution of polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 301 mPa · s. Separate 12.0 g of the polyamic acid solution into a 100 mL conical flask placed in a stirrer, add 13.2 g of NMP and 10.8 g of BCS, and stir with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (B-4) . [0110] <Production of Liquid Crystal Cell for Evaluation of Liquid Crystal Alignment> A method for producing a liquid crystal cell for evaluating liquid crystal alignment is shown below. A liquid crystal cell having a structure of a liquid crystal display element having an FFS method is produced. First, a substrate with electrodes is prepared. The substrate was a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. An IZO electrode constituting a counter electrode is formed on the substrate as a first layer. On the counter electrode of the first layer, a SiN (silicon nitride) film formed by a CVD method is formed as a second layer. The SiN film of the second layer has a film thickness of 500 nm and functions as an interlayer insulating film. On the second layer of the SiN film, a comb-shaped pixel electrode formed by patterning the IZO film is arranged as the third layer to form two pixels, namely, a first pixel and a second pixel. The size of each pixel is 10 mm in length and about 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer. The pixel electrode of the third layer is the same as the one described in Japanese Unexamined Patent Publication No. 2014-77845 (Japanese Laid-Open Patent Publication), and has a comb-like shape formed by arranging a plurality of “く” -shaped electrode elements bent at a central portion. The width in the width direction of each electrode element is 3 μm, and the interval between the electrode elements is 6 μm. The pixel electrode forming each pixel is formed by arranging a plurality of “く” -shaped electrode elements bent at the central portion. Therefore, the shape of each pixel is not rectangular, but includes the same shape as the electrode element. "く" similar shape. Each pixel is divided up and down with its central curved portion as a boundary, and has a first region on the upper side and a second region on the lower side of the curved portion. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements constituting such pixel electrodes are different. That is, when the direction of a line segment of a polarizing plane of polarized ultraviolet rays described later is projected onto a substrate as a reference, the electrode element of the pixel electrode is formed at an angle (clockwise) of + 10 ° in the first region of the pixel. In the second region, the electrode element of the pixel electrode is formed at an angle (clockwise) of -10 °. That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane turning) of the liquid crystal in the substrate plane induced by the voltage application between the pixel electrode and the counter electrode are mutually opposite. Constructed in the opposite direction. [0111] Next, the liquid crystal alignment agent obtained in the synthesis example and the comparative synthesis example was filtered with a 1.0 μm filter, and then applied to the prepared substrate with electrodes by spin coating. Next, it was dried on a hot plate set at 70 ° C for 90 seconds. Next, UPL-L050121S1S-APW01, an exposure device made by Ushio Electric Co., Ltd., was used to irradiate the substrate with linearly polarized light from the vertical direction through the wavelength selection filter and polarizer. At this time, the direction of the line segment of the polarizing plane of the polarized ultraviolet rays projected onto the substrate is set so that the direction of the polarizing plane becomes a direction inclined by 10 ° with respect to the third-layer IZO comb-shaped electrode. Next, an IR (infrared) -type oven set at 230 ° C. was fired for 30 minutes to obtain a substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm that was subjected to the alignment treatment. In addition, as a counter substrate, a glass substrate having a columnar spacer having a height of 4 μm having an ITO electrode formed therein was also formed in the same manner as described above, and a polyimide liquid crystal alignment film with an alignment treatment was obtained. Of the substrate. The two substrates with a liquid crystal alignment film are used as a group, and a sealant is printed on the one substrate to retain the liquid crystal injection port. The other substrate is opposed to each other with the liquid crystal alignment film surface and is projected on the substrate The directions of the line segments of the polarized surface of the polarized ultraviolet light are paralleled to be bonded and pressed. Then, the sealant was hardened to produce an empty cell with a cell spacing of 4 μm. Liquid crystal MLC-7026-100 (negative liquid crystal manufactured by Merck) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell of the FFS method. Then, the obtained liquid crystal cell was heated at 120 ° C for 30 minutes, and left at 23 ° C for a while, and then used for evaluation of liquid crystal alignment. [0112] <Assessment of Liquid Crystal Orientation> Using this liquid crystal cell, an AC voltage of 16 VPP at a frequency of 30 Hz at a frequency of 168 hours was applied in a constant temperature environment of 70 ° C. After that, the pixel electrode and the counter electrode of the liquid crystal cell are brought into a short-circuited state, and the state is left at 23 ° C. for a while. After being placed, the liquid crystal cell is placed between two polarizing plates arranged with the polarizing axis vertical, and the backlight is turned on without an applied voltage, and the brightness of the transmitted light is adjusted to the minimum The arrangement angle of the liquid crystal cell. Then, the rotation angle from the angle at which the liquid crystal cell is rotated from the darkest angle in the second region of the first pixel to the darkest angle in the first region is calculated as the angle Δ. Similarly for the second pixel, the second region is compared with the first region and the same angle Δ is calculated. Then, an average value of the angle Δ values of the first pixel and the second pixel is calculated as the angle Δ of the liquid crystal cell. If the value of the angle Δ of the liquid crystal cell is less than 1.0 °, it is defined as “good”, and if the value of the angle Δ is 1.0 ° or more, it is defined as “bad” for evaluation. [Example 1] The liquid crystal alignment agent (A-1) obtained in Synthesis Example 1 was used to prepare a liquid crystal cell as described above. Irradiation of polarized ultraviolet light was performed using a high-pressure mercury lamp through a wavelength-selective filter: 240LCF and a 254nm-type polarizing plate. The amount of polarized ultraviolet radiation was measured by using a UV light meter UVD-S254SB made by Ushio Electric Co., Ltd., and the wavelength was changed from 600 to 1500 mJ / cm at a wavelength of 254 nm. 2 It is implemented within the range of 3 to produce three or more liquid crystal cells with different amounts of polarized ultraviolet radiation. As a result of evaluating the alignment of the liquid crystals for these liquid crystal cells, the angle Δ is the optimal amount of polarized ultraviolet radiation to be 1200 mJ / cm 2 The angle Δ is good at 0.13 °. [Examples 2 to 6] Except for using the liquid crystal alignment agent obtained in Synthesis Examples 2 to 6, the same method as in Example 1 was used to evaluate the liquid crystal alignment. [Comparative Examples 1 to 4] Except for using the liquid crystal alignment agent obtained in Comparative Synthesis Examples 1 to 4, the same method as in Example 1 was used to evaluate the liquid crystal alignment. [0116] Table 1 shows the results of the evaluation of the polarized ultraviolet radiation amount and the liquid crystal alignment when the angle Δ was the best when the liquid crystal alignment agent obtained in the synthesis example and the comparative synthesis example was used. [0117] [0118] As shown in Table 1, in Examples 1 to 6, the difference (angle Δ) between the alignment azimuth angles before and after the AC drive is less than 1.0 °, which is good, so the display quality of the liquid crystal display element is improved. On the other hand, in Comparative Examples 1 to 4, the angle Δ was 1.0 ° or more and it was defective. It was confirmed that the liquid crystal display element manufactured by the method of the present invention exhibits very excellent afterimage characteristics. [Industrial Applicability] [0119] A substrate for a lateral electric field drive type liquid crystal display device manufactured using the composition of the present invention or a lateral electric field drive type liquid crystal display device having the substrate has excellent long-term stability of liquid crystal alignment. It is suitable for large-screen and high-definition LCD TVs. In addition, the liquid crystal alignment film system produced by the method of the present invention can also be used in a variable phase shifter using liquid crystal, and the variable phase shifter system can be suitably used in, for example, an antenna capable of changing the resonance frequency.