TWI801351B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

(B)成分：具有下述式(2)之結構的二胺

(C)成分：具有選自下述式(a)及下述式(b)的至少1種結構的二胺

The present invention relates to a liquid crystal alignment film containing a polymer having an aromatic heterocycle and a primary amino group and a secondary amino group in its structure, and a liquid crystal alignment agent capable of forming such a liquid crystal alignment film. The above-mentioned aromatic heterocycle and the above-mentioned primary amino group and secondary amino group are preferably formed when the liquid crystal alignment film is fired. Specifically, the liquid crystal alignment agent is selected from the following polyamic acid and its imide At least one polymer of polyimide; the polyamic acid is a skeleton containing at least one diamine selected from the following component (A) and the following component (B), and containing the following component (C) The diamine component of diamine, and the reactant of tetracarboxylic dianhydride. In addition, the definitions of the symbols in each chemical formula are as described in the specification. (A) Component: Diamine having at least one structure selected from the following formula (1-1) and the following formula (1-2)

(B) Component: Diamine having a structure of the following formula (2)

(C) Component: Diamine having at least one structure selected from the following formula (a) and the following formula (b)

Description

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

[0001] The present invention relates to a liquid crystal alignment agent used in the manufacture of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film.

[0002] A liquid crystal display element is known as a light-weight, thin display device with low power consumption. In recent years, even high-definition liquid crystal display elements used in mobile phones and tablet-type terminals that are rapidly expanding sharing have advanced to the point where higher display quality is required. [0003] A liquid crystal display element is formed by sandwiching a liquid crystal layer between a pair of transparent substrates equipped with electrodes. In the liquid crystal display element, in order to make the liquid crystal exhibit a desired alignment state between the substrates, an organic film made of organic materials is used as a liquid crystal alignment film. That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on the surface that is in contact with the liquid crystal of the substrate that sandwiches the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates. [0004] In recent years, liquid crystal display elements used in portable applications such as smart phones and mobile phones have been used. In these applications, in order to secure as many display surfaces as possible, the width of the sealant to be used between the substrates to which the liquid crystal display element is attached must be narrower than in the past. Furthermore, for the above reasons, it is desirable to place the sealant at a position adjacent to the end of the liquid crystal alignment film having weak adhesion with the sealant, or on the upper portion of the liquid crystal alignment film. In this case, especially in the use under high temperature and high humidity conditions, water is likely to be mixed between the self-sealing agent and the liquid crystal alignment film, and display unevenness will occur near the frontal edge of the liquid crystal display element. [0005] In order to solve this problem, there has been a proposal of a liquid crystal alignment agent using an additive of a specific structure (refer to Patent Document 1). [Prior Art Document] [Patent Document] [0006] [Patent Document 1] International Publication No. 2015/072554

(式中，D表示2價碳數1~20的飽和烴基、不飽和烴基、芳香族烴基或雜環，D表示可具有種種取代基，E表示單鍵或2價碳數1~20的飽和烴基、不飽和烴基、芳香族烴基或者雜環，F表示單鍵或醚鍵(-O-)、酯鍵(-OCO-、-COO-)，m表示1或0，R表示熱脱離基，*表示與其他原子的鍵結。) (B)成分：具有下述式(2)之結構的二胺 　　[0019]

(式中，X₁ 表示選自由-O-、-NQ¹ -、-CONQ¹ -、-NQ¹ CO-、-CH₂ O-及-OCO-所成群的至少1種2價有機基，Q¹ 表示氫原子或碳數1至3的烷基，X₂ 表示單鍵或選自由碳數1至20的脂肪族烴基、非芳香族環式烴基及芳香族烴基所成群的至少1種2價有機基，X₃ 表示單鍵或選自由-O-、-NQ² -、-CONQ² -、-NQ² CO-、-COO-、-OCO-及-O(CH₂ )_m -(m表示1至5的整數)所成群的至少1種2價有機基，Q² 表示氫原子或碳數1至3的烷基，X₄ 表示芳香族雜環，*表示與其他原子的鍵結)。 (C)成分：具有選自下述式(a)及下述式(b)的至少1種結構之二胺 　　[0020]

(式中，X¹ 為氧原子或硫原子，A¹ ~A³ 各獨立為氫原子或碳數1~3的烴基，碳數的合計為1~9。又，*表示與其他原子的鍵結。) [發明之效果] 　　[0021] 藉由使用本發明之液晶配向劑，可得到提高密封劑與液晶配向膜之接著性，在高溫高濕條件下，可抑制液晶顯示元件的額緣附近之顯示不均的產生之液晶配向膜。因此，具有藉此所得之液晶配向膜的液晶顯示元件因提高密封劑與液晶配向膜的接著性，而可解決額緣附近的顯示不均，適用於在大畫面的高精細液晶顯示上。[Problems to be Solved by the Invention] [0007] However, in recent years, further improvement in the adhesion between the liquid crystal alignment film and the sealant has been demanded. Wherein, known in by the characteristic improvement of sealant, it is difficult to have the adhesion characteristic of sealant and liquid crystal alignment film concurrently, and the moisture permeability prevention characteristic of sealant, from above-mentioned point of view, by the liquid crystal alignment film Feature improvement is expected. Therefore, the present invention aims to provide a liquid crystal alignment agent that improves the adhesion between the sealant and the liquid crystal alignment film, and can suppress the generation of uneven display near the frontal edge of the liquid crystal display element under high temperature and high humidity conditions. [Means to solve the problem] The present inventors intend to solve the above-mentioned problems and carry out detailed examination results, by using a liquid crystal alignment film of a polymer containing a specific aromatic heterocycle, a primary amine group, and a secondary amine group, And complete the present invention. [0011] The first aspect of the present invention to achieve the above object is a liquid crystal alignment film, which is characterized in that it contains a polymer having an aromatic heterocycle, a primary amino group, and a secondary amino group in the structure. The second aspect of the present invention that achieves the above-mentioned purpose is the liquid crystal alignment film of the first aspect, which is characterized in that it is a film made of fired products, the skeleton of the aforementioned aromatic heterocycle and the aforementioned primary amino group and The above-mentioned secondary amino group is contained in the structure generated by firing. [0013] The third aspect of the present invention to achieve the above object is the liquid crystal alignment film of the first aspect or the second aspect, which is characterized in that the aforementioned aromatic heterocycle is a pyridine skeleton, a benzimidazole skeleton or an imidazole skeleton. [0014] The fourth aspect of the present invention to achieve the above object is the liquid crystal alignment film of the second aspect, which is characterized in that the fired product is produced at a firing temperature of 100°C to 300°C. [0015] A fifth aspect of the present invention that achieves the above-mentioned purpose is a liquid crystal display element, which is characterized in that it is equipped with any liquid crystal alignment film as in the first aspect to the fourth aspect. [0016] The sixth aspect of the present invention to achieve the above object is a liquid crystal alignment agent, which is used to obtain any liquid crystal alignment film in the first aspect to the fourth aspect. The 7th aspect of the present invention that achieves the above-mentioned purpose is the liquid crystal alignment agent of the 6th aspect, which is characterized in that it contains the following polymer, which is selected from the following polyamic acid and imides thereof At least one polyimide containing at least one diamine selected from the following component (A) and the following component (B), and two of the skeletons containing the following component (C) The reactant of diamine component of amine and tetracarboxylic dianhydride. (A) component: diamine having at least one structure selected from the following formula (1-1) and following formula (1-2) [0018]

(In the formula, D represents a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring with a divalent carbon number of 1 to 20, D represents a variety of substituents, and E represents a single bond or a saturated hydrocarbon group with a divalent carbon number of 1 to 20. Hydrocarbon group, unsaturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic ring, F represents a single bond or ether bond (-O-), ester bond (-OCO-, -COO-), m represents 1 or 0, R represents a thermal detachment group , * represents the bonding with other atoms.) (B) component: have the diamine of the structure of following formula (2) [0019]

(wherein, X ₁ represents at least one divalent organic group selected from the group consisting of -O-, -NQ ¹ -, -CONQ ¹ -, -NQ ¹ CO-, -CH ₂ O-, and -OCO-, Q ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbons, X ₂ represents a single bond or at least one selected from the group consisting of aliphatic hydrocarbon groups, non-aromatic cyclic hydrocarbon groups, and aromatic hydrocarbon groups having 1 to 20 carbons A divalent organic group, X ₃ represents a single bond or is selected from -O-, -NQ ² -, -CONQ ² -, -NQ ² CO-, -COO-, -OCO- and -O(CH ₂ ) _m -( m represents an integer of 1 to 5), at least one divalent organic group grouped, Q ² represents a hydrogen atom or an alkyl group having 1 to 3 carbons, X ₄ represents an aromatic heterocyclic ring, and * represents a bond with another atom Knot). (C) Component: diamine having at least one structure selected from the following formula (a) and following formula (b)

(In the formula, X ¹ is an oxygen atom or a sulfur atom, A ¹ to A ³ are each independently a hydrogen atom or a hydrocarbon group with 1 to 3 carbons, and the total number of carbons is 1 to 9. Also, * represents a bond with other atoms knot.) [Effect of the invention] [0021] By using the liquid crystal alignment agent of the present invention, the adhesion between the sealant and the liquid crystal alignment film can be improved, and under high temperature and high humidity conditions, the liquid crystal display element near the frontal edge can be suppressed. The liquid crystal alignment film that produces uneven display. Therefore, the liquid crystal display element with the obtained liquid crystal alignment film can solve the display unevenness near the forehead by improving the adhesion between the sealant and the liquid crystal alignment film, and is suitable for large-screen high-definition liquid crystal display.

[0031] 對於上述式(a)，X¹ 為氧原子或硫原子，A¹ ~A³ 各獨立為氫原子或碳數1~3的烴基，碳數的合計為1~9。又，對於上述式(a)及上述式(b)，*表示與其他原子的鍵結。 　　[0032] 進行與1級胺基之環化反應，產生芳香族雜環的結構，例如可舉出如以下的結構。 　　[0033]

[0034] 式中，D表示2價碳數1~20的飽和烴基、不飽和烴基、芳香族烴基或雜環，D表示可具有種種取代基。又，E表示單鍵或2價碳數1~20的飽和烴基、不飽和烴基、芳香族烴基或者雜環，F表示單鍵或醚鍵(-O-)、酯鍵(-OCO-、-COO-)。m為1或0。R為上述式(a)所示結構。 　　[0035] 燒成步驟後之被膜厚度若過厚時，在液晶顯示元件之消費電力的層面上來看為變的不利，若過薄時，液晶顯示元件的信賴性有降低之情況，故較佳為5nm~300nm，更佳為10nm~100nm。使液晶呈水平配向或傾斜配向時，將燒成後的被膜藉由摩擦或偏光紫外線照射等公知方法進行配向處理。 　　[0036] ＜芳香族雜環＞ 　　含於本發明之液晶配向膜中的聚合物之上述芳香族雜環的例子，可舉出吡咯環、呋喃環、噻吩環、咪唑環、吡唑環、噁唑環、異噁唑環、噻唑環、異噻唑環等五員環芳香族雜環；吡啶環、嘧啶環、噠嗪環、吡嗪環、三嗪環等六員環芳香族雜環；喹啉、異喹啉、香豆素、吲哚、苯並咪唑、苯並呋喃等多環芳香族雜環化合物。 　　[0037] 上述中亦由可使本發明的效果更顯著之觀點來看，以吡啶環、咪唑環、苯並咪唑環為佳，以咪唑環、苯並咪唑環為特佳。 　　[0038] 前述芳香族雜環存在於含於前述液晶配向劑的聚合物中時亦可發揮本發明之效果，但由上述觀點來看，於液晶配向膜之燒成時，形成芳香族雜環骨架者為佳。且，含於液晶配向劑的聚合物中已經存在之芳香族雜環與於燒成時所形成的芳香族雜環並存者為佳。 　　[0039] ＜聚合物＞ 　　本發明之液晶配向劑及使用其所得之液晶配向膜中所含有的聚合物若為結構中具有芳香族雜環及1級胺基及2級胺基者即可，並無特別限定，但由所得之液晶顯示元件的特性及信賴性之觀點來看，由選自二胺成分與四羧酸衍生物成分的反應物之聚醯亞胺前驅體及其醯亞胺化物之聚醯亞胺的至少1種聚合物為佳。 　　[0040] 此所謂的聚醯亞胺前驅體係指聚醯胺酸或聚醯胺酸酯。 　　[0041] ＜二胺＞ 　　作為本發明之液晶配向劑及使用此所得之液晶配向膜中所含有的聚合物，以選自由聚醯亞胺前驅體及其醯亞胺化物的聚醯亞胺的至少1種聚合物者為佳，但使用於該製造的二胺成分中，可使用選自由具有產生芳香族雜環的結構之二胺(以下亦稱為特定二胺1)及將芳香族雜環於結構中具有的二胺(以下亦稱為特定二胺2)所成群的至少1種二胺及具有產生1級胺基或2級胺基的結構之二胺(以下亦稱為特定二胺3)。 　　[0042] 對於各二胺，如以下詳述。 　　[0043] ＜特定二胺1＞ 　　特定二胺1為具有選自以下式(1-1)、式(1-2)的結構。 　　[0044]

[0045] 上述式(1-1)中，D表示2價碳數1~20的飽和烴基、不飽和烴基、芳香族烴基或雜環，D表示可具有種種取代基。又，上述式(1-2)中，E為單鍵或2價碳數1~20的飽和烴基、不飽和烴基、芳香族烴基或者雜環，F表示單鍵或醚鍵(-O-)、酯鍵(-OCO-、-COO-)。上述式(1-1)中，m為1或0。上述式(1-1)及上述式(1-2)中，R表示熱脱離基。 　　[0046] 上述式(1-1)及上述式(1-2)中之*表示與其他原子的鍵結。與胺基鍵結時，胺基的取代位置並無特別限定，由合成難易度或試藥的獲得性之觀點來看，若將醯胺鍵作為基準時，以間位或對位的位置為佳，由液晶配向性的觀點來看，以對位的位置為特佳。又，對於不具有以熱脱離基保護的胺基之胺基苯，同樣地將醯胺鍵作為基準時，間位或對位的位置為佳，由溶解性的觀點來看，以間位的位置為佳，由液晶配向性之觀點來看，以對位的位置為佳。又，不具有-NHR的胺基苯之氫亦可由有機基或氟等鹵素原子等。 　　[0047] 又，上述式(1-1)的*為可與相同上述式(1-1)的結構或上述式(1-2)的結構鍵結，亦可藉著其他原子，與上述式(1-1)的結構或上述式(1-2)的結構鍵結。 　　[0048] 上述式(1-1)中之D，上述式(1-2)中之E與上述定義同樣，並無詳細特別限定，藉由作為原料使用的二羧酸或四羧酸二酐等結構，可選擇出種種結構。作為D，由溶解性之觀點來看，以2價烴基等為佳，直鏈伸烷基或環狀伸烷基等為較佳例子可舉出，該烴基可具有不飽和鍵。又，由液晶配向性或電特性的觀點來看，以2價芳香族烴基或雜環等為佳。由液晶配向性之觀點來看，D不具有取代基者為佳，由溶解性的觀點來看，氫原子可由羧酸基或氟原子等所取代者為佳。 　　[0049] ＜特定二胺2＞ 　　特定二胺2為具有以下式(2)的結構。 　　[0050]

[0051] 上述式(2)中，X₁ 為選自-O-、-NQ¹ -、-CONQ¹ -、-NQ¹ CO-、-CH₂ O-及-OCO-所成群的至少1種2價有機基，Q¹ 為氫原子或碳數1至3的烷基，X₂ 為單鍵或選自由碳數1至20的脂肪族烴基、非芳香族環式烴基及芳香族烴基所成群的至少1種2價有機基，X₃ 為單鍵或選自由-O-、-NQ² -、-CONQ² -、-NQ² CO-、-COO-、-OCO-、及-O(CH₂ )_m -(m為1至5的整數)所成群的至少1種2價有機基，Q² 為氫原子或碳數1至3的烷基，X₄ 為芳香族雜環。 　　[0052] *表示與其他原子的鍵結。與胺基鍵結時，二個胺基(-NH₂ )之鍵結位置並無限定。具體為對於側鏈的鍵結基(X₁ )，苯環上的第2、3位置、第2、4位置、第2、5位置、第2、6位置、第3、4位置、第3、5位置可舉出。此等中，亦由合成聚醯胺酸時的反應性之觀點及合成二胺化合物時的容易性來看，二個胺基之鍵結位置以第2、4位置、第2、5位置、第3、5位置為特佳。 　　[0053] 又，*表示與相同上述式(2)的結構鍵結，或亦可藉著其他原子與上述式(2)的結構鍵結。 　　[0054] X₁ 為選自由-O-、-NQ¹ -、-CONQ¹ -、-NQ¹ CO-、-CH₂ O-、及-OCO-所成群的至少1種2價有機基。其中亦以-O-、-NQ¹ -、-CONQ¹ -、-NQ¹ CO-為佳。且，Q¹ 為氫原子或碳數1至3的烷基，較佳為氫原子或甲基。 　　[0055] X₂ 為單鍵或選自由碳數1至20的脂肪族烴基、非芳香族環式烴基及芳香族烴基所成群的至少1種2價有機基。 　　[0056] 碳數1至20的脂肪族烴基可為直鏈狀亦可為分支。又，亦可具有不飽和鍵。較佳為碳數1至10的脂肪族烴基。 　　[0057] X₃ 為單鍵或選自由-O-、-NQ² -、-CONQ² -、-NQ² CO-、-COO-、-OCO-及-O(CH₂ )_m -(m為1至5的整數)所成群的至少1種2價有機基，較佳為單鍵、-O-、-CONQ² -、-NQ² CO-、-COO-、-OCO-、-O(CH₂ )_m -(m為1至5的整數)。最佳為單鍵、-OCO-或-OCH₂ -。且，Q¹ 為氫原子或碳數1至3的烷基，較佳為氫原子或甲基。 　　[0058] X₄ 為芳香族雜環。該例示及較佳結構與上述者相同。 　　[0059] 特佳為X₁ 、X₂ 、X₃ 、X₄ 及n的組合，如下述表1至表3所示。且，Q¹ 及Q² 與上述定義同意義。 　　[0060]

[0061]

[0062]

[0063] ＜特定二胺3＞ 　　特定二胺3為具有產生1級胺基或2級胺基的結構之二胺，於結構中具有藉由熱脱離基經保護的胺基之結構。如此結構並無特別限定，但由容易進行熱脱離等觀點來看，含有選自以下結構的至少1種結構者為佳。 　　[0064]

[0065] 上述式(a)中，X¹ 為氧原子或硫原子，A¹ ~A³ 各獨立為氫原子或碳數1~3的烴基，碳數合計為1~9。又，上述式(a)及上述式(b)中，*表示與其他原子的鍵結。 　　[0066] 上述式(a)中，X¹ 為氧原子或硫原子，以氧原子為佳。A¹ ~A³ 各獨立為氫原子或碳數1~3的烴基，以碳數1為佳。且，碳數合計為1~9，以3~6為佳。又，上述式(a)及上述式(b)中，*表示與其他原子的鍵結。 　　[0067] 作為結構中具有選自上述式(a)、上述式(b)的至少1種結構的二胺，例如可舉出以下結構之二胺。且，式中之「Boc」為tert-丁氧基羰基。 　　[0068]

[0069] ＜具有與聚合無關的胺基之二胺＞ 　　欲得到本發明之液晶配向膜的液晶配向劑之製造中，具有產生1級胺基或2級胺基的結構之二胺，即雖使用結構中具有藉由熱脱離基經保護的胺基之結構的二胺，即使用未經保護，且具有與聚合無關的胺基之二胺亦可。如此二胺如以下所例示。 　　[0070]

[0071] ＜其他二胺＞ 　　製造作為含於本發明之液晶配向劑的聚合物而適用的聚醯亞胺前驅體時，對於達到本發明之效果的限度下，可含有特定二胺以外的二胺(以下亦稱為其他二胺)。如此二胺如以下一般式(3)所示。 　　[0072]

[0073] 對於上述式(3)，Y為來自二胺的2價有機基，該結構並無特別限定。Y的結構之具體例子若要表示，可舉出下述式(Y-1)~式(Y-99)。 　　[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

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[0088]

[0089] 上述式(Y-90)中，m、n各為1至11的整數，m+n為2至12的整數，上述式(Y-95)中，h為1~3的整數，上述式(Y-92)及上述式(Y-98)中，j為0至3的整數。 　　[0090] ＜四羧酸二酐＞ 　　製造作為含於本發明之液晶配向劑的聚合物而適用的聚醯亞胺前驅體時所使用的四羧酸二酐為下述式(4)所示。 　　[0091]

[0092] 對於上述式(4)，X表示來自四羧酸衍生物的4價有機基，該結構並無特別限定。聚醯亞胺前驅體中，X可混在2種類以上。X的具體例子若要表示，可舉出下述式(X-1)~下述式(X-44)的結構。 　　[0093] 又，製造聚醯胺酸酯時，可使用相當於此所舉出的四羧酸二酐的種種結構之二羧酸二酯而製造。 　　[0094]

[0095]

[0096]

[0097]

[0098] 上述式(X-1)中之R₁ ~R₄ 各獨立為氫原子、鹵素原子、碳數1~6的烷基、碳數2~6的烯基、炔基或者苯基。R₁ ~R₄ 為容積高的結構時，因可能使液晶配向性降低，以氫原子、甲基、乙基為較佳，以氫原子或甲基為特佳。 　　[0099] 上述式(4)中，X由單體之獲得性的觀點來看，含有選自上述式(X-1)~上述式(X-14)的結構者為佳。 　　[0100] 由更提高所得之液晶配向膜的信賴性來看，X的結構如上述式(X-1)~上述式(X-7)及上述式(X-10)，僅由脂肪族基所成的結構為佳，上述式(X-1)所示結構為較佳。進一步欲顯示良好液晶配向性，作為X的結構，以下述式(X1-1)或下述式(X1-2)為更佳。 　　[0101]

[0102] ＜液晶配向劑＞ 　　本發明之液晶配向劑為具有前述聚醯亞胺前驅體或其醯亞胺化聚合物(以下稱為特定結構之聚合物)溶解於有機溶劑中之溶液形態。特定結構的聚合物之分子量在重量平均分子量以2,000~500,000為佳,較佳為5,000~300,000，更佳為8,000~100,000。又，數平均分子量較佳為1,000~250,000，更佳為2,500~150,000，特佳為4,000 ~50,000。 　　[0103] 使用於本發明的液晶配向劑之聚合物濃度，可藉由所要形成的塗膜厚度之設定而做適宜變更，以形成均勻且無缺陷的塗膜的觀點來看，以1重量%以上者為佳，由溶液的保存安定性之觀點來看以10重量%以下者為較佳。特佳的聚合物之濃度為2~8質量%。 　　[0104] 含於使用於本發明的液晶配向劑之有機溶劑若為可均勻地溶解特定結構之聚合物者即可，並無特別限定。若要舉出該具體例子，可舉出N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-甲基己內醯胺、2-吡咯啶酮、N-乙烯基-2-吡咯啶酮、二甲基亞碸、二甲基碸、γ-丁內酯、1,3-二甲基-咪唑啉酮、3-甲氧基-N,N-二甲基丙烷醯胺等。這些可1種或混合2種以上使用。又，即使為在單獨無法均勻溶解聚合物的溶劑，若不會析出聚合物的範圍，可混合於上述有機溶劑。其中以使用N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮或γ-丁內酯者為佳。 　　[0105] 又，含於液晶配向劑的有機溶劑為，除如上述溶劑以外，一般使用並用塗布液晶配向劑時可提高塗佈性或塗膜表面平滑性的溶劑之混合溶劑，對於本發明之液晶配向劑，亦可適用如此混合溶劑。併用的有機溶劑之具體例子可舉出下述，但並未限定於此等例子。 　　[0106] 例如可舉出乙醇、異丙醇、1-丁醇、2-丁醇、異丁基醇、tert-丁基醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊基醇、tert-戊基醇、3-甲基-2-丁醇、新戊基醇、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、2,6-二甲基-4-庚醇、1,2-乙烷二醇、1,2-丙烷二醇、1,3-丙烷二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊烷二醇、2-甲基-2,4-戊烷二醇、2-乙基-1,3-己二醇、二異丙基醚、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、2,6-二甲基-4-庚酮、4,6-二甲基-2-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、伸丙基碳酸酯、伸乙基碳酸酯、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-(己基氧基)乙醇、糠基醇、二乙二醇、丙二醇、二乙二醇單乙基醚、二乙二醇單甲基醚、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-甲氧基丙酸甲基、3-乙氧基丙酸乙酯、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、乳酸甲基酯、乳酸乙酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊基酯、下述式[D-1]~下述式[D-3]所示溶劑等。 　　[0107]

[0108] 上述式[D-1]中，D¹ 表示碳數1~3的烷基，上述式[D-2]中，D² 表示碳數1~3的烷基，上述式[D-3]中，D³ 表示碳數1~4的烷基。 　　[0109] 其中作為較佳溶劑的組合，可舉出N-甲基-2-吡咯啶酮與γ-丁內酯與乙二醇單丁基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁基醚、N-乙基-2-吡咯啶酮與丙二醇單丁基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與4-羥基-4-甲基-2-戊酮與二乙二醇二乙基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁基醚與二異丙基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁基醚與2,6-二甲基-4-庚醇、N-甲基-2-吡咯啶酮與γ-丁內酯與二丙二醇二甲基醚等。如此溶劑之種類及含有量可配合液晶配向劑之塗佈裝置、塗佈條件、塗佈環境等做適宜選擇。 　　[0110] 本發明之液晶配向劑中，如上述者以外，若不損害本發明之效果的範圍下，可添加本發明所記載的聚合物以外的聚合物、欲改變液晶配向膜的介電率或導電性等電特性為目的之介電體或者導電物質、提高液晶配向膜與基板之密著性為目的之矽烷偶合劑、作為液晶配向膜時的膜之硬度或提高緻密度為目的之交聯性化合物、進一步在燒成塗膜時藉由聚醯亞胺前驅體之加熱使醯亞胺化可有效率地進行為目的之醯亞胺化促進劑等。 　　[0111] 其他，本發明之液晶配向劑中亦可添加對於基板的塗膜密著性可提高的矽烷偶合劑等添加劑，又亦可添加其他樹脂成分。 　　[0112] 作為提高液晶配向膜與基板之密著性的化合物，可舉出含有官能性矽烷之化合物或含有環氧基之化合物，例如可舉出3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲丙基三甲氧基矽烷、3-脲丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽基丙基三伸乙基三胺、N-三甲氧基矽基丙基三伸乙基三胺、10-三甲氧基矽基-1,4,7-三氮雜癸烷、10-三乙氧基矽基-1,4,7-三氮雜癸烷、9-三甲氧基矽基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽基-3,6-二氮雜壬基乙酸酯、N-苯甲基-3-胺基丙基三甲氧基矽烷、N-苯甲基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧基伸乙基)-3-胺基丙基三甲氧基矽烷、N-雙(氧基伸乙基)-3-胺基丙基三乙氧基矽烷、乙二醇二縮水甘油基醚、聚乙二醇二縮水甘油基醚、丙二醇二縮水甘油基醚、三丙二醇二縮水甘油基醚、聚丙二醇二縮水甘油基醚、新戊二醇二縮水甘油基醚、1,6-己二醇二縮水甘油基醚、甘油二縮水甘油基醚、2,2-二溴新戊二醇二縮水甘油基醚、1,3,5,6-四縮水甘油基-2,4-己二醇、N,N,N’,N’,-四縮水甘油基-m-二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷或N,N,N’,N’,-四縮水甘油基-4、4’-二胺基二苯基甲烷等。 　　[0113] 又，於本發明之液晶配向劑中，可添加可提高膜之機械性強度的如以下之添加物。 　　[0114]

[0115]

[0116] 這些添加劑對於含於液晶配向劑之聚合物成分100質量份而言，以0.1~30質量份為佳。未達0.1質量份時無法達到令人滿意的效果，若超過30質量份時，會降低液晶之配向性，故較佳為0.5質量份~20質量份。 　　[0117] ＜液晶顯示元件＞ 　　本發明之液晶顯示元件為藉由上述方法自本發明之液晶配向劑得到附有液晶配向膜之基板，藉由摩擦處理等配向處理後，藉由既知的方法得到液晶顯示元件。 　　[0118] 液晶顯示元件的液晶單元之製造方法並無特別限定，若要舉出一例子，其為將形成液晶配向膜的1對基板將液晶配向膜面放置於內側，較佳為夾著1μm~ 30μm，更佳為2μm~10μm的間隔物而設置後，將周圍以密封劑固定，注入液晶使其封止的方法為一般。對於封入液晶的方法並無特別限制，將製作的液晶單元內經減壓後，注入液晶的真空法、滴入液晶後進行封止的滴下法等可例示。如上述，由本發明之液晶配向劑所得之液晶配向膜具有優良特性，故可作為VA、TN、STN、TFT、橫向電場型等液晶顯示元件、更可作為強介電性及反強介電性之液晶顯示元件用的液晶配向膜使用。 [實施例] 　　[0119] 以下對於本發明舉出實施例等做具體說明，但本發明並未受限於此等實施例。且化合物、溶劑的簡稱如以下所示。 　　NMP：N-甲基-2-吡咯啶酮 　　GBL：γ-丁內酯 　　BCS：丁基溶纖劑 　　DA-1：下述結構式(DA-1) 　　DA-2：下述結構式(DA-2) 　　DA-3：下述結構式(DA-3) 　　DA-4：下述結構式(DA-4) 　　DA-5：下述結構式(DA-5) 　　DA-6：下述結構式(DA-6) 　　DA-7：下述結構式(DA-7) 　　DA-8：下述結構式(DA-8) 　　DA-9：下述結構式(DA-9) 　　DA-10：下述結構式(DA-10) 　　CA-1：下述結構式(CA-1) 　　CA-2：下述結構式(CA-2) 　　CA-3：下述結構式(CA-3) 　　CA-4：下述結構式(CA-4) 　　[0120]

[0121]

[0122]

[0123] ＜黏度＞ 　　對於合成例，聚合物溶液之黏度使用E型黏度計TVE-22H(東機產業公司製)，以試樣量1.1mL、錐形轉子TE-1(1°34’、R24)、溫度25℃下測定。 　　[0124] ＜聚醯亞胺之醯亞胺化率的測定＞ 　　於合成例中之聚醯亞胺的醯亞胺化率係如下述測定。將聚醯亞胺粉末30mg放入NMR(核磁共振)試樣管(NMR取樣試管標準，f5(草野科學公司製))中，添加重氫化二甲基亞碸(DMSO-d6，0.05質量%TMS(四甲基矽烷)混合品)(0.53ml)，施予超音波使其完全溶解。將該溶液以NMR測定機(JNW-ECA500)(日本電子數據公司製)測定500MHz之質子NMR。醯亞胺化率係以來自在醯亞胺化前後不產生變化的結構之質子作為基準質子而決定，使用該質子之吸收峰積分值與來自9.5ppm~10.0ppm附近出現的醯胺酸之NH基的質子吸收峰積分值而藉由以下式子求得。 　　[0125] 　　醯亞胺化率(%)=(1-α･x/y)×100 　　對於上述式，x為來自醯胺酸的NH基之質子吸收峰積分值，y為基準質子的吸收峰積分值，α為聚醯胺酸(醯亞胺化率為0%)時，醯胺酸對於1個NH基質子的基準質子之個數比例。 　　[0126] (實施例1) 　　於攪拌裝置及附有氮導入管之1L四口燒瓶中，86.0g(352mmol)之DA-1、53.4g(95.9mmol)之DA-2及76.5g(191mmol)之DA-3，加入NMP 1580g，一邊送入氮氣一邊攪拌並使其溶解。將該二胺溶液在水冷下一邊攪拌，一邊添加93.2g(416mmol)之CA-1，再加入NMP 168g，氮環境下在40℃進行3小時攪拌。再將CA-2的28.2g (143mmol)添加，進一步加入NMP 160g，氮環境下於23℃進行4小時攪拌，得到聚醯胺酸之溶液(PAA-1)。該聚醯胺酸之溶液的溫度25℃中之黏度為200mPa･s。 　　[0127] 於放有攪拌子的200mL三角燒瓶中，放入聚醯胺酸溶液(PAA-1)30.7g，加入NMP 9.07g、GBL 26.2g、含有1質量%的3-環氧丙氧基丙基三乙氧基矽烷之NMP溶液3.93g及BCS 17.4g，在磁力攪拌器下進行2小時攪拌後得到聚醯胺酸之溶液(A-1)。 　　[0128] (實施例2) 　　於放有攪拌子的3L三角燒瓶中，放入在實施例1所得之聚醯胺酸溶液(PAA-1)800g，加入NMP 700g、乙酸酐69.7g、吡啶18.0g，在室溫下進行30分鐘攪拌後，在55℃進行3小時反應。將該反應溶液投入於5600g的甲醇中，過濾出所得之沈澱物。將該沈澱物以甲醇洗淨後，在溫度60℃下減壓乾燥，得到聚醯亞胺之粉末。該聚醯亞胺的粉末之醯亞胺化率為75%。 　　[0129] 放有攪拌子的300mL三角燒瓶中，放入該聚醯亞胺之粉末20.4g，加入NMP115g，在50℃進行20小時攪拌並使其溶解。進一步將該溶液16.3g放入100mL三角燒瓶中，加入NMP 5.49g、GBL 14.3g、含有1質量%的3-環氧丙氧基丙基三乙氧基矽烷之NMP溶液 2.15g及BCS 9.56g，以磁力攪拌器進行2小時攪拌後得到聚醯亞胺的溶液(A-2)。 　　[0130] (合成例1) 　　於附有攪拌裝置及氮導入管之200mL四口燒瓶中，放入2.20g(9.00mmol)之DA-1、2.04g(5.97mmol)之DA-4、1.62g(15.0mmol)之DA-5，NMP 59.3g，一邊送入氮氣一邊攪拌使其溶解。將該二胺溶液在水冷下一邊攪拌一邊添加6.32g(28.1mmol)之CA-1，再加入NMP 30.0g，在氮環境下於40℃進行3小時攪拌後得到聚醯胺酸之溶液(PAA-2)。該聚醯胺酸之溶液溫度25℃中之黏度為220mPa･s。 　　[0131] 在放有攪拌子的200mL三角燒瓶中，取出21.1g的該聚醯胺酸之溶液(PAA-2)，加入NMP 2.20g、GBL 15.3g、含有1質量%的3-環氧丙氧基丙基三乙氧基矽烷之NMP溶液2.30g及BCS 10.2g，以磁力攪拌器進行2小時攪拌後得到聚醯胺酸之溶液(B-1)。 　　[0132] (合成例2) 　　於放有攪拌子的500mL之三角燒瓶中，放入90.0g的在合成例1所得之聚醯胺酸的溶液(PAA-2)，加入NMP 45.0g、乙酸酐8.14g、吡啶2.10g，在室溫進行30分鐘攪拌後，在55℃進行3小時反應。將該反應溶液投入於600g之甲醇中，過濾所得之沈澱物。該沈澱物以甲醇洗淨後，以溫度60℃進行減壓乾燥後得到聚醯亞胺之粉末。該聚醯亞胺的粉末之醯亞胺化率為67%。 　　[0133] 於放有攪拌子之300mL三角燒瓶中，取出該聚醯亞胺之粉末5.50g，加入NMP 40.3g，在50℃進行20小時攪拌並使其溶解。再將該溶液25.0g放入放有攪拌子的200mL三角燒瓶，加入NMP 5.30g、GBL 20.0g、含有1質量%的3-環氧丙氧基丙基三乙氧基矽烷之NMP溶液3.00g及BCS 13.3g，以磁力攪拌器進行2小時攪拌後得到聚醯亞胺之溶液(B-2)。 　　[0134] (合成例3) 　　於附有攪拌裝置及氮導入管的200mL四口燒瓶中，放入0.540g(4.99mmol)之DA-5、2.12g(8.75mmol)之DA-6、0.826g(2.50mmol)之DA-7、3.80g(8.75mmol)之DA-8，加入NMP 41.3g，一邊送氮一邊攪拌使其溶解。將該二胺溶液在水冷下一邊攪拌，一邊添加3.12g(12.4mmol)之CA-3，再添加NMP 17.8g，在氮環境下60℃進行3小時攪拌。再添加2.42g(12.3mmol)之CA-2，進一步添加NMP 14.1g，在氮環境下於40℃進行4小時攪拌，得到聚醯胺酸之溶液。該聚醯胺酸之溶液在溫度25℃的黏度為115mPa･s。 　　[0135] 於放有攪拌子的200mL三角燒瓶中，放入該聚醯胺酸之溶液20.6g，加入NMP 10.6g、GBL 20.6g、含有1質量%的3-環氧丙氧基丙基三乙氧基矽烷之NMP溶液3.09g及BCS 13.7g，以磁力攪拌器進行2小時攪拌後得到聚醯胺酸之溶液(B-3)。 　　[0136] (合成例4) 　　於附有攪拌裝置及氮導入管之200mL四口燒瓶中，放入3.18g(8.00mmol)之DA-3、2.38g(6.00mmol)之DA-9、1.79g(6.00mmol)之DA-10，加入NMP 66.2g，一邊送入氮一邊攪拌並使其溶解。將該二胺溶液在水冷下一邊攪拌，一邊添加4.25g(19.5mmol)之CA-4，再添加NMP 18.9g，在氮環境下50℃進行15小時攪拌，得到聚醯胺酸之溶液。該聚醯胺酸之溶液的溫度在25℃時的黏度為264mPa･s。 　　[0137] 於放有攪拌子的100mL三角燒瓶中，放入該聚醯胺酸之溶液15.3g，加入NMP 0.300g、GBL 10.3g、含有1質量%的3-環氧丙氧基丙基三乙氧基矽烷之NMP溶液1.54g及BCS 6.86g，以磁力攪拌器進行2小時攪拌後得到聚醯胺酸之溶液(B-4)。 　　[0138] (實施例3) 　　於放有攪拌子之50mL三角燒瓶中，加入在實施例1所得之聚醯胺酸的溶液(A-1)5.42g、在合成例1所得之聚醯胺酸的溶液(B-1)5.41g，以磁力攪拌器進行2小時攪拌後得到液晶配向劑(A-3)。 　　[0139] (實施例4) 　　於放有攪拌子的50mL三角燒瓶中，加入在實施例2所得之聚醯亞胺的溶液(A-2)5.50g、在合成例2所得之聚醯亞胺的溶液(B-2)5.51g，以磁力攪拌器進行2小時攪拌後得到液晶配向劑(A-4)。 　　[0140] (實施例5) 　　於放有攪拌子的50mL三角燒瓶中，加入在合成例1所得之聚醯胺酸的溶液(B-1)5.42g、在合成例3所得之聚醯胺酸的溶液(B-3)5.42g，以磁力攪拌器進行2小時攪拌後得到液晶配向劑(A-5)。 　　[0141] (實施例6) 　　於放有攪拌子的50mL三角燒瓶中，加入在實施例1所得之聚醯胺酸的溶液(A-1)5.62g、在合成例4所得之聚醯胺酸的溶液(B-4)5.62g，以磁力攪拌器進行2小時攪拌後得到液晶配向劑(A-6)。 　　[0142] ＜密封接著力之評估＞ 　　將在實施例及合成例所得之液晶配向劑以1.0μm的濾器經過濾後，旋塗於附有透明電極之玻璃基板上，在80℃之加熱板上進行2分鐘乾燥後，在230℃進行20分鐘燒成後得到膜厚100nm之塗膜。準備如此所得之2片基板，於一方基板的液晶配向膜面上散布4μm珠子間隔物後，滴入密封劑(協立化學製XN-1500T)。其次，將另一方的基板之液晶配向膜面作為內側，將基板的重疊寬度為1cm下進行貼合。此時，調整密封劑滴入量至貼合後的密封劑之直徑約3mm。將貼合的2片基板以夾具固定後，在120℃下進行1小時熱硬化，製造出接著性評估用之試樣。 　　[0143] 其次，將製作的試樣以島津製作所製之桌上形精密萬能試驗機AGS-X 500N，固定上下基板之端部分後，自基板中央部上部推入，將剝離時的力(N)作為密封接著力而評估。 　　[0144] (實施例7~12) 　　將在實施例1~6所得之液晶配向劑(A-1)~(A-6)各以1.0μm之濾器進行過濾後，如上述記載製造出接著性評估用之試樣而評估密封接著力，其結果如表4所示。 　　[0145] (比較例1~4) 　　將在合成例1~4所得之液晶配向劑(B-1)~(B-4)各以1.0μm的濾器進行過濾後，如上述記載製造出接著性評估用試樣而評估密封接著力之結果如表4所示。 　　[0146]

[0147] 使用實施例所記載的液晶配向劑時，密封接著力為高表示良好。 　　[0148] (實施例13) 　　於附有攪拌裝置及氮導入管的200mL之四口燒瓶中，加入4.30g(17.6mmol)之DA-1、2.67g(4.80mmol)之DA-2、3.27g(9.57mmol)之DA-4，加入NMP 75.1g，一邊送入氮一邊攪拌並使其溶解。將該二胺溶液在水冷下一邊攪拌，一邊添加4.66g(20.7mmol)之CA-1，進一步添加NMP 9.34g，在氮環境下40℃下進行3小時攪拌。進一步添加1.78g(9.08mmol)CA-2，進一步添加NMP 8.00g，在氮環境下23℃下進行4小時攪拌，得到聚醯胺酸之溶液。該聚醯胺酸之溶液的溫度25℃中之黏度為304mPa･s。 　　[0149] 於放有攪拌子的500mL之三角燒瓶中，放入該聚醯胺酸之溶液90.0g，加入NMP 79.0g、乙酸酐 7.92g、吡啶 2.04g，在室溫下進行30分鐘攪拌後，在55℃進行3小時反應。將該反應溶液投入於700g之甲醇中，過濾所得之沈澱物。該沈澱物以甲醇洗淨後，以溫度60℃進行減壓乾燥後得到聚醯亞胺之粉末。該聚醯亞胺的粉末之醯亞胺化率為70%。 　　[0150] 於放有攪拌子之200mL三角燒瓶中，加入該聚醯亞胺之粉末6.07g，NMP 44.5g，在50℃進行20小時攪拌後使其溶解。再將該溶液20.3g放於放有攪拌子之200mL三角燒瓶，加入NMP 4.37g、GBL 16.2g、含有1質量%的3-環氧丙氧基丙基三乙氧基矽烷之NMP溶液 2.43g及BCS 10.8g，以磁力攪拌器進行2小時攪拌後得到聚醯亞胺之溶液(A-7)。 　　[0151] (實施例14) 　　於附有攪拌裝置及氮導入管之200mL的四口燒瓶中，加入4.30g(17.6mmol)之DA-1、2.67g(4.80mmol)之DA-2、1.91g(4.80mmol)之DA-3、1.64g(4.80mmol)之DA-4、NMP 77.1g，一邊送入氮一邊進行攪拌使其溶解。將該二胺溶液在水冷下一邊攪拌一邊添加4.66g(20.7mmol)之CA-1，再加入NMP 8.88g，氮環境下在40℃進行3小時攪拌。且，添加1.71g(8.69mmol)之CA-2，再加入NMP 8.00g，在氮環境下23℃下進行4小時攪拌，得到聚醯胺酸之溶液。該聚醯胺酸的溶液在溫度25之黏度為312mPa･s。 　　[0152] 於放有攪拌子的500mL之三角燒瓶中，加入該聚醯胺酸之溶液90.0g，加入NMP 79.0g、乙酸酐 7.02g、吡啶 1.81g，在室溫下進行30分鐘攪拌後，在55℃進行3小時反應。將該反應溶液投入於700g之甲醇中，將所得之沈澱物過濾。該沈澱物以甲醇洗淨後，以溫度60℃進行減壓乾燥後得到聚醯亞胺之粉末。該聚醯亞胺的粉末之醯亞胺化率為71%。 　　[0153] 於放有攪拌子的200mL三角燒瓶中，放入該聚醯亞胺之粉末6.03g，加入NMP 44.2g，在50℃進行20小時攪拌並使其溶解。再將該溶液21.0g放入放有攪拌子之200mL三角燒瓶中，加入NMP 4.48g、GBL 16.8g、含有1質量%的3-環氧丙氧基丙基三乙氧基矽烷之NMP溶液2.52g及BCS 11.2g，以磁力攪拌器進行2小時攪拌後得到聚醯亞胺之溶液(A-8)。 　　[0154] (合成例5) 　　於附有攪拌裝置及氮導入管之1L四口燒瓶中，放入4.30g(17.6mmol)之DA-1、5.73g(14.3mmol)之DA-3，NMP 73.6g，一邊送入氮一邊進行攪拌並使其溶解。將該二胺溶液在水冷下一邊進行攪拌，一邊添加4.66g(20.7mmol)之CA-1，再添加NMP 9.69g，在氮環境下40℃下進行3小時攪拌。再添加1.50g(7.65mmol)之CA-2，再加入NMP 8.53g，在氮環境下23℃下進行4小時攪拌，得到聚醯胺酸之溶液。該聚醯胺酸之溶液在溫度25℃之黏度為290mPa･s。 　　[0155] 於放有攪拌子的500mL之三角燒瓶中，放入該聚醯胺酸之溶液90.0g，加入NMP 79.0g、乙酸酐 8.16g、吡啶 2.10g，在室溫下進行30分鐘攪拌後，在55℃進行3小時反應。將該反應溶液投入於700g之甲醇中，過濾所得之沈澱物。該沈澱物以甲醇洗淨後，以溫度60℃進行減壓乾燥後得到聚醯亞胺之粉末。該聚醯亞胺的粉末之醯亞胺化率為72%。 　　[0156] 於放有攪拌子的200mL三角燒瓶中，放入該聚醯亞胺粉末6.10g，加入NMP44.7g，在50℃進行20小時攪拌並使其溶解。再將該溶液25.0g於放有攪拌子之200mL三角燒瓶，加入NMP 4.90g、GBL 19.8g、含有1質量%的3-環氧丙氧基丙基三乙氧基矽烷之NMP溶液 3.00g及BCS 13.3g，以磁力攪拌器進行2小時攪拌後得到聚醯亞胺之溶液(B-5)。 　　[0157] ＜液晶配向性之評估＞ 　　以下表示欲評估液晶配向性的液晶單元之製作方法。 　　[0158] 製作出具備FFS方式之液晶顯示元件的構成之液晶單元。首先準備附有電極之基板。基板的尺寸為30mm×35mm，厚度為0.7mm之玻璃基板。於基板上作為第1層，構成對向電極之IZO電極形成於全面。於第1層對向電極上，作為第2層，藉由CVD法而形成經成膜的SiN(氮化矽)膜。第2層的SiN膜之膜厚為100nm，作為層間絕緣膜發揮其功能。於第2層的SiN膜上，配置作為第3層，對IZO膜製圖所形成的梳齒狀畫素電極，形成第1畫素及第2畫素的2個畫素。各畫素的尺寸為縱10mm、橫約5mm。此時，第1層的對向電極與第3層之畫素電極藉由第2層的SiN膜之作用，成電性絕緣體。 　　[0159] 第3層的畫素電極為中央部分彎曲之成為く字形狀的電極要素以複數配列方式構成，具有梳齒狀之形狀。各電極要素的橫向方向之寬度為3μm，電極要素間之間隔為6μm。形成各畫素之畫素電極為具備中央部分彎曲的成為く字形狀之電極要素以複數配列方式構成，故各畫素之形狀並非長方形狀，與電極要素同樣地中央部分為彎曲之粗字的像く字之形狀。而各畫素為將該中央彎曲部分作為境界使其分割為上下部，具有彎曲部分的上側之第1區域與下側的第2區域。 　　[0160] 若比較各畫素的第1區域與第2區域時，構成這些的畫素電極之電極要素的形成方向成為相異者。即，將後述液晶配向膜之摩擦方向作為基準時，在畫素的第1區域，畫素電極的電極要素成為+10°之角度(順時鐘方向)，在畫素的第2區域中，畫素電極的電極要素成為-10°之角度(順時鐘方向)。即，在各畫素的第1區域與第2區域中，藉由畫素電極與對向電極之間的輸入電壓，所引起的液晶的在基板面內之轉動動作(平面內･開關)的方向互相成反方向而構成。 　　[0161] 其次，將在實施例及合成例所得之液晶配向劑以1.0μm的濾器進行過濾後，於準備的附有上述電極之基板上以旋塗塗佈。在80℃的加熱板上進行2分鐘乾燥後，以230℃的熱風循環式烤箱進行20分鐘燒成，得到膜厚60nm之聚醯亞胺膜。將該聚醯亞胺膜以人造纖維布進行摩擦(輥直徑：120mm、輥轉動數：500rpm、移動速度：30mm/sec、推入長：0.3mm、摩擦方向：對第3層IZO梳齒電極呈10°的傾斜方向)後，於純水中進行1分鐘超音波照射並進行洗淨，以吹空氣方式除去水滴。其後，在80℃進行15分鐘乾燥，得到附有液晶配向膜之基板。又，作為對向基板，於裏面形成ITO電極，具有高度4μm的柱狀間隔物之玻璃基板亦與上述同樣地形成聚醯亞胺膜，以與上述同樣程序下，得到施予配向處理之附有液晶配向膜之基板。將這些2片附有液晶配向膜之基板作為1組，於基板上殘留液晶注入口的形式下印刷密封劑，將另1片基板面向液晶配向膜面，貼合成摩擦方向成為逆平行。其後，使密封劑硬化，製作晶胞間隙為4μm的空胞。藉由於該空胞以減壓注入法，注入液晶MLC-3019(默克公司製)，密封注入口，得到FFS方式之液晶單元。其後將所得之液晶單元在120℃進行1小時加熱，並在23℃放置一晩後使用於液晶配向性的評估上。 　　[0162] 使用該液晶單元，在60℃的恆溫環境下，以頻率數30Hz的9VPP之交流電壓輸入190小時。其後，使液晶單元的畫素電極與對向電極之間成為短路現像，直接在室溫下放置一天。 　　[0163] 放置後，將液晶單元設置在配置成偏光軸為直交的2片偏光板之間，在無輸入電壓的狀態下打上背光，調整液晶單元的配置角度使透過光的亮度為最小。而自第1畫素的第2區域變得最暗的角度至第1區域變得最暗的角度而轉動液晶單元時的轉動角度作為角度Δ而算出。對於第2畫素亦同樣地，比較第2區域與第1區域，算出同樣角度Δ。而將第1畫素與第2畫素的角度Δ值之平均值作為液晶單元的角度Δ而算出。即，該角度越小液晶配向性越良好。 　　[0164] (實施例15~18) 　　將各在實施例2、4、13、14所得之液晶配向劑(A-2)、(A-4)、(A-7)及(A-8)以1.0μm的濾器過濾後，製作出如上述記載的接著性評估用試樣，並評估密封接著力，其結果及上述液晶單元的角度Δ之結果如表5所示。 　　[0165] (比較例5) 　　將在合成例5所得之液晶配向劑(B-5)以1.0μm的濾器過濾後，如上述記載，製作出接著性評估用試樣，評估密封接著力的結果及上述液晶單元之角度Δ結果如表5所示。 　　[0166]

[0167] 使用實施例所記載的液晶配向劑時，其密封接著力高，且老化後的液晶單元之角度Δ小，其液晶配向性亦良好。 [產業上可利用性] 　　[0168] 本發明之液晶配向劑對於可確保多數顯示面的狹額緣液晶顯示元件，藉由提高密封劑與液晶配向膜之接著性，解決額緣附近的顯示不均而在產業上為有用。[Mode of Carrying Out the Invention] [0022] Each constituent element of the liquid crystal alignment film of the present invention will be described in detail below. [0023] <Liquid Crystal Alignment Film> The liquid crystal alignment film of the present invention is a polymer containing an aromatic heterocycle, primary amine groups, and secondary amine groups in its structure. The liquid crystal alignment film of the present invention is, after coating and firing the liquid crystal alignment agent on the substrate to form a film (hereinafter also referred to as the film) of the polymer contained in the liquid crystal alignment agent, by rubbing or photoirradiation, etc. to perform alignment treatment. In cases such as vertical alignment applications, it can also be used as a liquid crystal alignment film without alignment treatment. [0025] As the substrate used at this time, as long as it is a highly transparent substrate, other than a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the manufacturing process, it is preferable to use a substrate formed of ITO electrodes and the like for liquid crystal driving. In addition, in a reflective liquid crystal display element, if only a single-sided substrate is used, an opaque substrate such as a silicon wafer can also be used, and a light-reflecting material such as aluminum can also be used as an electrode in this case. [0026] The coating method of the liquid crystal alignment agent is not particularly limited. In industry, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally carried out. As other coating methods, there are dip, roll coater, slit coater, spinner, etc., which can be used according to the purpose. After the liquid crystal alignment agent is coated on the substrate, the solvent is evaporated at 100°C to 300°C, preferably at 100°C to 250°C, preferably at 150°C to 250°C, by heating means such as a heating plate. Form a polymer film (hereinafter this step is referred to as a firing step). For the aforementioned firing step, the thermal detachment group of the protective amine group in the polymer is detached by heat, producing highly reactive 1-level and 2-level amine groups, and by this part and other in the polymer The site undergoes a cyclization reaction to generate an aromatic heterocycle. As a result, the liquid crystal alignment film of the present invention is obtained, which is preferable from the viewpoint of the effect of the present invention and the storage stability of the liquid crystal alignment agent. The preferred one contained in the polymer of the present invention is a structure of an amine group bonded to a thermal detachment group, such as shown below. [0030]

For above-mentioned formula (a), X ¹ is an oxygen atom or a sulfur atom, A ¹ ～A ³ are each independently a hydrocarbon group of hydrogen atom or carbon number 1～3, and the total of carbon number is 1～9. In addition, in the above-mentioned formula (a) and the above-mentioned formula (b), * represents a bond with another atom. Carry out the cyclization reaction with primary amino group, produce the structure of aromatic heterocycle, for example can enumerate as following structure. [0033]

In formula, D represents the saturated hydrocarbyl of divalent carbon number 1～20, unsaturated hydrocarbyl, aromatic hydrocarbyl or heterocycle, and D represents and can have various substituting groups. In addition, E represents a single bond or a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring with a divalent carbon number of 1 to 20, and F represents a single bond or an ether bond (-O-), an ester bond (-OCO-, - COO-). m is 1 or 0. R is a structure represented by the above formula (a). If the film thickness after the firing step is too thick, it will be unfavorable in terms of the power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element will decrease, so it is better 5nm~300nm, more preferably 10nm~100nm. When aligning the liquid crystal horizontally or obliquely, the fired coating is subjected to alignment treatment by known methods such as rubbing or polarized ultraviolet irradiation. <Aromatic Heterocycle> Examples of the above-mentioned aromatic heterocycle contained in the polymer of the liquid crystal alignment film of the present invention include pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxa Five-membered aromatic heterocycles such as azole ring, isoxazole ring, thiazole ring, and isothiazole ring; six-membered aromatic heterocycles such as pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, and triazine ring; Polycyclic aromatic heterocyclic compounds such as morphine, isoquinoline, coumarin, indole, benzimidazole, and benzofuran. In the above, also from the viewpoint that the effect of the present invention can be made more remarkable, the pyridine ring, the imidazole ring, and the benzimidazole ring are preferred, and the imidazole ring and the benzimidazole ring are particularly preferred. When the above-mentioned aromatic heterocycle exists in the polymer contained in the above-mentioned liquid crystal alignment agent, the effect of the present invention can also be brought into play, but from the above point of view, when the liquid crystal alignment film is fired, the aromatic heterocycle is formed Skeleton is better. Furthermore, it is preferable that the aromatic heterocycles already present in the polymer contained in the liquid crystal alignment agent coexist with the aromatic heterocycles formed during firing. <Polymer> The liquid crystal alignment agent of the present invention and the polymer contained in the liquid crystal alignment film obtained by using it can be as long as it has an aromatic heterocycle, a primary amino group, and a secondary amino group in its structure. It is not particularly limited, but from the viewpoint of the characteristics and reliability of the obtained liquid crystal display element, the polyimide precursor and its imide selected from the reactant of the diamine component and the tetracarboxylic acid derivative component At least one polymer of polyimide compound is preferred. This so-called polyimide precursor system refers to polyamic acid or polyamic acid ester. <Diamine> As the liquid crystal alignment agent of the present invention and the polymer contained in the liquid crystal alignment film obtained by using the same, polyimides selected from polyimide precursors and imides thereof At least one type of polymer is preferable, but for the diamine component to be produced, diamines selected from diamines having a structure generating an aromatic heterocycle (hereinafter also referred to as specific diamine 1) and aromatic heterocycles can be used. At least one diamine grouped with diamines (hereinafter also referred to as specific diamine 2) in the ring structure and diamines having a structure that produces primary or secondary amine groups (hereinafter also referred to as specific diamines) Diamines 3). For each diamine, as detailed below. <Specific diamine 1> Specific diamine 1 has a structure selected from the following formula (1-1) and formula (1-2). [0044]

In the above formula (1-1), D represents a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring with a divalent carbon number of 1 to 20, and D represents that it may have various substituents. Also, in the above formula (1-2), E is a single bond or a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring with a divalent carbon number of 1 to 20, and F represents a single bond or an ether bond (-O-) , Ester bond (-OCO-, -COO-). In the above formula (1-1), m is 1 or 0. In the above formula (1-1) and the above formula (1-2), R represents a thermal detachment group. * in above-mentioned formula (1-1) and above-mentioned formula (1-2) represents the bonding with other atoms. When bonding with an amine group, the substitution position of the amine group is not particularly limited. From the viewpoint of the ease of synthesis or the availability of reagents, if the amide bond is used as a benchmark, the meta-position or para-position is From the viewpoint of liquid crystal alignment, the para position is particularly preferable. Also, for aminobenzene that does not have an amine group protected by a thermal detachment group, when the amide bond is used as a reference in the same way, the meta-position or the para-position is preferable. From the viewpoint of solubility, the meta-position The position of the position is better, and from the point of view of liquid crystal alignment, the position of the opposite position is better. Also, the hydrogen of the aminobenzene not having -NHR may be an organic group or a halogen atom such as fluorine. Again, the * of above-mentioned formula (1-1) is that can be bonded with the structure of same above-mentioned formula (1-1) or the structure of above-mentioned formula (1-2), also can be by other atom, with above-mentioned formula The structure of (1-1) or the structure of the above formula (1-2) is bonded. D in the above-mentioned formula (1-1), the E in the above-mentioned formula (1-2) is the same as the above-mentioned definition, without detailed special limitation, by dicarboxylic acid or tetracarboxylic dianhydride used as raw material Various structures can be selected. As D, from the viewpoint of solubility, a divalent hydrocarbon group is preferable, and a linear alkylene group or a cyclic alkylene group is preferable, and the hydrocarbon group may have an unsaturated bond. Also, from the viewpoint of liquid crystal alignment or electrical properties, divalent aromatic hydrocarbon groups, heterocyclic rings, and the like are preferable. From the viewpoint of liquid crystal alignment, it is preferable that D has no substituent, and from the viewpoint of solubility, it is preferable that a hydrogen atom can be substituted by a carboxylic acid group or a fluorine atom. <Specific diamine 2> Specific diamine 2 has the structure of following formula (2). [0050]

In the above-mentioned formula (2), X ₁ is at least 1 selected from the groups of -O-, -NQ ¹ -, -CONQ ¹ -, -NQ ¹ CO-, -CH ₂ O- and -OCO- A divalent organic group, Q ¹ is a hydrogen atom or an alkyl group with 1 to 3 carbons, X ₂ is a single bond or is selected from an aliphatic hydrocarbon group with 1 to 20 carbons, a non-aromatic cyclic hydrocarbon group and an aromatic hydrocarbon group A group of at least one divalent organic group, X ₃ is a single bond or is selected from -O-, -NQ ² -, -CONQ ² -, -NQ ² CO-, -COO-, -OCO-, and -O (CH ₂ ) _m - (m is an integer of 1 to 5) grouped with at least one divalent organic group, Q ² is a hydrogen atom or an alkyl group having 1 to 3 carbons, and X ₄ is an aromatic heterocyclic ring. [0052] * represents a bond with other atoms. When bonding with an amine group, the bonding position of the two amine groups (-NH ₂ ) is not limited. Specifically, for the bonding group (X ₁ ) of the side chain, the 2nd, 3rd, 2nd, 4th, 2nd, 5th, 2nd, 6th, 3rd, 4th, and 3rd positions on the benzene ring , 5 positions can be cited. Among these, also from the viewpoint of reactivity when synthesizing polyamic acid and the ease of synthesizing diamine compounds, the bonding positions of the two amine groups are the 2nd and 4th positions, the 2nd and 5th positions, The 3rd and 5th positions are especially good. Again, * represents to be bonded with the structure of identical above-mentioned formula (2), or also can be by other atom and the structure bond of above-mentioned formula (2). [0054] X ₁ is at least one divalent organic group selected from the group consisting of -O-, -NQ ¹ -, -CONQ ¹ -, -NQ ¹ CO-, -CH ₂ O-, and -OCO-. Among them, -O-, -NQ ¹ -, -CONQ ¹ -, and -NQ ¹ CO- are also preferable. And, ^Q1 is a hydrogen atom or an alkyl group with 1 to 3 carbons, preferably a hydrogen atom or a methyl group. [0055] _X2 is a single bond or at least one divalent organic group selected from aliphatic hydrocarbon groups with carbon numbers of 1 to 20, non-aromatic cyclic hydrocarbon groups and aromatic hydrocarbon groups. [0056] The aliphatic hydrocarbon group with 1 to 20 carbons can be linear or branched. Moreover, it may have an unsaturated bond. It is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. X ₃ is a single bond or is selected from -O-, -NQ ² -, -CONQ ² -, -NQ ² CO-, -COO-, -OCO- and -O(CH ₂ ) _m -(m is an integer of 1 to 5), at least one divalent organic group grouped, preferably a single bond, -O-, -CONQ ² -, -NQ ² CO-, -COO-, -OCO-, -O( CH ₂ ) _m - (m is an integer of 1 to 5). Most preferred is a single bond, -OCO- or -OCH ₂ -. And, ^Q1 is a hydrogen atom or an alkyl group with 1 to 3 carbons, preferably a hydrogen atom or a methyl group. X ₄ is an aromatic heterocycle. The exemplary and preferred structures are the same as those described above. Especially preferred is the combination of X ₁ , X ₂ , X ₃ , X ₄ and n, as shown in Table 1 to Table 3 below. Also, ^Q1 and ^Q2 have the same meaning as defined above. [0060]

[0061]

[0062]

<Specific diamine 3> Specific diamine 3 is a diamine having a structure that generates a primary amine group or a secondary amine group, and has a structure of an amine group protected by a thermal detachment group in the structure. Such a structure is not particularly limited, but it is preferable to contain at least one structure selected from the following structures from the viewpoint of easiness of thermal detachment. [0064]

In the above-mentioned formula (a), X ¹ is an oxygen atom or a sulfur atom, A ¹ ~ A ³ are each independently a hydrocarbon group of a hydrogen atom or a carbon number of 1 ~ 3, and the total number of carbons is 1 ~ 9. In addition, in the above-mentioned formula (a) and the above-mentioned formula (b), * represents a bond with another atom. In above-mentioned formula (a), ^X is oxygen atom or sulfur atom, is preferably with oxygen atom. A ¹ to A ³ are each independently a hydrogen atom or a hydrocarbon group with 1 to 3 carbons, preferably 1 carbon. And, the total number of carbons is 1-9, preferably 3-6. In addition, in the above-mentioned formula (a) and the above-mentioned formula (b), * represents a bond with another atom. As the diamine having at least one structure selected from the above-mentioned formula (a) and the above-mentioned formula (b) in the structure, for example, the diamine of the following structure can be enumerated. Also, "Boc" in the formula is tert-butoxycarbonyl. [0068]

<Diamines having amino groups not related to polymerization> In the manufacture of liquid crystal alignment agents to obtain the liquid crystal alignment film of the present invention, diamines having a structure that produces primary or secondary amino groups, that is, although A diamine having a structure of an amine group protected by a thermal detachment group in the structure may be used, and a diamine which is not protected and has an amine group not involved in the polymerization may also be used. Such diamines are exemplified below. [0070]

<Other diamines> When producing a polyimide precursor suitable as a polymer contained in the liquid crystal alignment agent of the present invention, diamines other than specific diamines may be contained as long as the effect of the present invention is achieved. Amines (hereinafter also referred to as other diamines). Such a diamine is represented by the following general formula (3). [0072]

[0073] In the above formula (3), Y is a divalent organic group derived from diamine, and the structure is not particularly limited. Specific examples of the structure of Y include the following formula (Y-1) to formula (Y-99). [0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

In above-mentioned formula (Y-90), m, n are respectively the integer of 1 to 11, and m+n is the integer of 2 to 12, and in above-mentioned formula (Y-95), h is the integer of 1～3, In said formula (Y-92) and said formula (Y-98), j is an integer of 0-3. <Tetracarboxylic dianhydride> The tetracarboxylic dianhydride used in the manufacture of a polyimide precursor suitable as a polymer contained in the liquid crystal alignment agent of the present invention is represented by the following formula (4) . [0091]

In the above formula (4), X represents a tetravalent organic group derived from a tetracarboxylic acid derivative, and the structure is not particularly limited. In the polyimide precursor, two or more types of X can be mixed. Specific examples of X include structures of the following formula (X-1) to the following formula (X-44), if they are to be represented. Again, when making polyamic acid ester, can use the dicarboxylic acid diester that is equivalent to the various structures of the tetracarboxylic dianhydrides mentioned here and make. [0094]

[0095]

[0096]

[0097]

R in above-mentioned formula (X- ₁ ) ～R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbons, an alkenyl group with 2 to 6 carbons, an alkynyl group or a phenyl group. When R ₁ to R ₄ have a high-volume structure, hydrogen atoms, methyl groups, and ethyl groups are preferred, and hydrogen atoms or methyl groups are particularly preferred because they may reduce the alignment of liquid crystals. In above-mentioned formula (4), X is from the standpoint of the obtainability of monomer, it is better to contain the structure person selected from above-mentioned formula (X-1) ~ above-mentioned formula (X-14). From the perspective of improving the reliability of the liquid crystal alignment film obtained, the structure of X is as above-mentioned formula (X-1) ~ above-mentioned formula (X-7) and above-mentioned formula (X-10), only by aliphatic group The formed structure is preferable, and the structure represented by the above-mentioned formula (X-1) is more preferable. Further, in order to show good liquid crystal alignment, the structure of X is more preferably the following formula (X1-1) or the following formula (X1-2). [0101]

<Liquid Crystal Alignment Agent> The liquid crystal alignment agent of the present invention is in the form of a solution in which the aforementioned polyimide precursor or its imidized polymer (hereinafter referred to as a polymer with a specific structure) is dissolved in an organic solvent. The weight average molecular weight of the polymer with a specific structure is preferably 2,000-500,000, more preferably 5,000-300,000, more preferably 8,000-100,000. Also, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, and most preferably from 4,000 to 50,000. The polymer concentration used in the liquid crystal alignment agent of the present invention can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, 1% by weight The above is preferable, and it is more preferably 10% by weight or less from the viewpoint of storage stability of the solution. The particularly preferred polymer concentration is 2-8% by mass. [0104] The organic solvent contained in the liquid crystal alignment agent used in the present invention is not particularly limited as long as it can evenly dissolve a polymer with a specific structure. To give this specific example, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2 -Pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, dimethyl Dimethicone, γ-butyrolactone, 1,3-dimethyl-imidazolinone, 3-methoxy-N,N-dimethylpropanamide, etc. These can be used 1 type or in mixture of 2 or more types. Moreover, even if it is a solvent which cannot dissolve a polymer uniformly alone, it can be mixed with the above-mentioned organic solvent as long as the polymer does not precipitate. Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone. Also, the organic solvent contained in the liquid crystal alignment agent is, in addition to the above-mentioned solvents, generally used together with a mixed solvent that can improve the applicability or the smoothness of the surface of the coating film when coating the liquid crystal alignment agent, for the present invention The liquid crystal alignment agent is also applicable to such a mixed solvent. Specific examples of the organic solvent used in combination include the following, but are not limited to these examples. For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-pentanol, -Methyl-1-butanol, isoamyl alcohol, tert-pentyl alcohol, 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, 2,6-dimethyl-4-heptanol, 1,2- Ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol Diol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diisopropyl ether, dipropyl ether, Dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol Alcohol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2- Pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 4,6-dimethyl-2-heptanone, 3 -Ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol Diacetate, Propylene Carbonate, Ethylene Carbonate, 2-(Methoxymethoxy) Ethanol, Ethylene Glycol Monobutyl Ether, Ethylene Glycol Monoisoamyl Ether, Ethylene Glycol Mono Hexyl ether, 2-(hexyloxy)ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monobutyl 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 diacetate, di Ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, tri Ethylene 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, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropionate Ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropyl propionate, 3-methoxybutyl propionate, methyl lactate, ethyl lactate, lactic acid n - Propyl ester, n-butyl lactate, isopentyl lactate, solvents represented by the following formula [D-1] to the following formula [D-3], etc. [0107]

In above-mentioned formula [D-1], D ¹ represents the alkyl of carbon number 1 ~ 3, in above-mentioned formula [D-2], D ² represents the alkyl of carbon number 1 ~ 3, above-mentioned formula [D- 3], D ³ represents an alkyl group having 1 to 4 carbon atoms. Wherein as the combination of preferred solvent, can enumerate N-methyl-2-pyrrolidone and gamma-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4-hydroxy- 4-methyl-2-pentanone and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N- Methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone and γ-butyrolactone With dipropylene glycol dimethyl ether, etc. In this way, the type and content of the solvent can be properly selected in accordance with the coating device, coating conditions, and coating environment of the liquid crystal alignment agent. In the liquid crystal alignment agent of the present invention, other than the above, if it does not damage the scope of the effect of the present invention, polymers other than the polymers described in the present invention can be added to change the dielectric constant of the liquid crystal alignment film Dielectric or conductive substances for the purpose of electrical properties such as electrical conductivity, silane coupling agents for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, and the hardness of the film when used as a liquid crystal alignment film or the purpose of increasing the density. Linked compounds, further imidization accelerators for the purpose of efficiently carrying out imidization by heating the polyimide precursor when firing the coating film, etc. [0111] In addition, the liquid crystal alignment agent of the present invention can also add additives such as silane coupling agents that can improve the coating film adhesion of the substrate, and can also add other resin components. As the compound that improves the adhesiveness of liquid crystal alignment film and substrate, can enumerate the compound that contains functional silane or the compound that contains epoxy group, for example can enumerate 3-aminopropyltrimethoxysilane, 3 -aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Diethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxy Silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureapropyltrimethoxysilane, 3-ureapropyltriethoxysilane, N- Ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltrimethoxysilane, N-triethoxysilylpropyltrimethoxysilane Amine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4 ,7-Triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonylacetic acid ester, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylenyl)-3-aminopropyltrimethoxysilane, N-bis(oxyethylenyl) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol di Glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether , 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylylenediamine, 1,3-bis (N,N-diglycidylaminomethyl)cyclohexane or N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. [0113] Also, in the liquid crystal alignment agent of the present invention, the following additives that can improve the mechanical strength of the film can be added. [0114]

[0115]

[0116] These additives are preferably 0.1-30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. When it is less than 0.1 parts by mass, no satisfactory effect can be achieved, and when it exceeds 30 parts by mass, the alignment of liquid crystals will be reduced, so 0.5 parts by mass to 20 parts by mass is preferable. <Liquid crystal display element> The liquid crystal display element of the present invention is a substrate with a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention by the above method, and after alignment treatment such as rubbing treatment, it is obtained by a known method Liquid crystal display element. The manufacturing method of the liquid crystal unit of the liquid crystal display element is not particularly limited. To give an example, it is to place a pair of substrates forming the liquid crystal alignment film on the inner side of the liquid crystal alignment film, preferably sandwiching 1 μm ~ 30μm, more preferably 2μm~10μm spacer is installed, the surrounding is fixed with a sealant, and the method of injecting liquid crystal to seal it is common. The method of encapsulating liquid crystals is not particularly limited, and examples include a vacuum method of injecting liquid crystals after depressurizing the produced liquid crystal cell, and a dropping method of dropping liquid crystals and then sealing them. As mentioned above, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention has excellent properties, so it can be used as liquid crystal display elements such as VA, TN, STN, TFT, and transverse electric field type, and can be used as ferroelectricity and antiferroelectricity. Used in liquid crystal alignment film for liquid crystal display elements. [Examples] [0119] Hereinafter, the present invention will be specifically described with examples and the like, but the present invention is not limited to these examples. In addition, the abbreviations of the compounds and solvents are as follows. NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: Butyl cellosolve DA-1: The following structural formula (DA-1) DA-2: The following structural formula (DA-2) DA-3: the following structural 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 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) CA-2: the following structural formula (CA-2) CA-3: the following structural formula (CA-3) CA-4: the following structural formula Formula (CA-4) [0120]

[0121]

[0122]

<Viscosity> For the synthesis example, the viscosity of the polymer solution uses an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample size of 1.1 mL, a conical rotor TE-1 (1 ° 34 ', R24), measured at a temperature of 25°C. <Measurement of imidization ratio of polyimide> The imidization ratio of polyimide in the synthesis example was measured as follows. Put 30 mg of polyimide powder into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, f5 (manufactured by Kusano Science Co., Ltd.)), add deuterated dimethyl sulfide (DMSO-d6, 0.05% by mass TMS (Tetramethylsilane) mixture) (0.53ml), apply ultrasonic waves to dissolve completely. Proton NMR at 500 MHz was measured for this solution with an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Data Corporation). The imidization rate is determined by using the proton from the structure that does not change before and after imidization as the reference proton, using the integrated value of the absorption peak of the proton and the NH group from the amide that appears around 9.5ppm~10.0ppm The integrated value of the proton absorption peak can be obtained by the following formula. Imidization rate (%)=(1-α･x/y)×100 For the above formula, x is the integral value of the proton absorption peak derived from the NH group of amide acid, and y is the absorption peak of the reference proton Integral value, α is the ratio of the number of reference protons of amide acid to 1 NH group proton when polyamide acid (imidization rate is 0%). (Example 1) In a stirring device and a 1L four-necked flask with a nitrogen introduction tube, 86.0g (352mmol) of DA-1, 53.4g (95.9mmol) of DA-2 and 76.5g (191mmol) Add 1580g of NMP to DA-3, and stir while feeding nitrogen gas to dissolve it. While stirring this diamine solution under water cooling, 93.2 g (416 mmol) of CA-1 was added, and NMP 168 g was added thereto, and stirred at 40° C. for 3 hours under a nitrogen atmosphere. Further, 28.2 g (143 mmol) of CA-2 was added, and 160 g of NMP was further added, and stirred at 23° C. for 4 hours under a nitrogen atmosphere to obtain a polyamic acid solution (PAA-1). The viscosity of the polyamic acid solution at a temperature of 25°C is 200mPa･s. In a 200mL Erlenmeyer flask with a stirrer, 30.7g of polyamic acid solution (PAA-1) was put into it, and 9.07g of NMP, 26.2g of GBL, and 3-glycidoxyl containing 1% by mass were added. 3.93 g of NMP solution of propyltriethoxysilane and 17.4 g of BCS were stirred under a magnetic stirrer for 2 hours to obtain a polyamic acid solution (A-1). (Example 2) In the 3L Erlenmeyer flask with stirring bar, put into 800g of the polyamic acid solution (PAA-1) gained in Example 1, add NMP 700g, acetic anhydride 69.7g, pyridine 18.0g g. After stirring at room temperature for 30 minutes, the reaction was carried out at 55° C. for 3 hours. This reaction solution was poured into 5600 g of methanol, and the obtained deposit was filtered off. After washing this precipitate with methanol, it dried under reduced pressure at the temperature of 60 degreeC, and obtained the powder of polyimide. The imidization rate of this polyimide powder was 75%. [0129] Put 20.4 g of the polyimide powder into a 300 mL Erlenmeyer flask equipped with a stirrer, add 115 g of NMP, and stir and dissolve at 50° C. for 20 hours. Furthermore, 16.3 g of this solution was put into a 100 mL Erlenmeyer flask, and 5.49 g of NMP, 14.3 g of GBL, 2.15 g of an NMP solution containing 1% by mass of 3-glycidoxypropyltriethoxysilane, and 9.56 g of BCS were added. , A solution (A-2) of polyimide was obtained after stirring with a magnetic stirrer for 2 hours. (Synthesis Example 1) In a 200mL four-neck flask with a stirring device and a nitrogen introduction tube, put 2.20g (9.00mmol) of DA-1, 2.04g (5.97mmol) of DA-4, 1.62g (15.0 mmol) of DA-5, 59.3 g of NMP, and stirred while feeding nitrogen gas to dissolve it. Add 6.32g (28.1mmol) of CA-1 to this diamine solution while stirring under water cooling, then add 30.0g of NMP, and stir at 40°C for 3 hours under a nitrogen atmosphere to obtain a solution of polyamic acid (PAA -2). The viscosity of the polyamic acid solution at 25°C is 220mPa･s. In a 200mL Erlenmeyer flask equipped with a stirring bar, take out 21.1g of the polyamic acid solution (PAA-2), add 2.20g of NMP, 15.3g of GBL, and 3-epoxypropylene containing 1% by mass 2.30 g of NMP solution of oxypropyltriethoxysilane and 10.2 g of BCS were stirred with a magnetic stirrer for 2 hours to obtain a polyamic acid solution (B-1). (Synthesis Example 2) In a 500mL Erlenmeyer flask with a stirring bar, put 90.0g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 1, add NMP 45.0g, acetic anhydride 8.14 g and 2.10 g of pyridine were stirred at room temperature for 30 minutes, and then reacted at 55° C. for 3 hours. This reaction solution was poured into 600 g of methanol, and the obtained precipitate was filtered. After the precipitate was washed with methanol, it was dried under reduced pressure at a temperature of 60° C. to obtain a polyimide powder. The imidization rate of this polyimide powder was 67%. [0133] In a 300 mL Erlenmeyer flask equipped with a stirrer, 5.50 g of the polyimide powder was taken out, 40.3 g of NMP was added, and stirred at 50° C. for 20 hours to dissolve it. Then put 25.0 g of this solution into a 200 mL Erlenmeyer flask with a stirring bar, add 5.30 g of NMP, 20.0 g of GBL, and 3.00 g of an NMP solution containing 1% by mass of 3-glycidoxypropyltriethoxysilane And BCS 13.3g, stirred with a magnetic stirrer for 2 hours to obtain a polyimide solution (B-2). (Synthesis Example 3) In a 200mL four-neck flask with a stirring device and a nitrogen introduction tube, put 0.540g (4.99mmol) of DA-5, 2.12g (8.75mmol) of DA-6, 0.826g (2.50 mmol) of DA-7 and 3.80 g (8.75 mmol) of DA-8 were added with 41.3 g of NMP, and stirred while sending nitrogen to dissolve. While stirring this diamine solution under water cooling, 3.12 g (12.4 mmol) of CA-3 was added, and NMP 17.8 g was added, and it stirred at 60 degreeC under nitrogen atmosphere for 3 hours. Furthermore, 2.42 g (12.3 mmol) of CA-2 was added, NMP 14.1 g was further added, and it stirred at 40 degreeC for 4 hours under nitrogen atmosphere, and obtained the solution of the polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25°C is 115mPa･s. In a 200mL Erlenmeyer flask equipped with a stirrer, put 20.6g of the polyamic acid solution, add 10.6g of NMP, 20.6g of GBL, and 3-glycidoxypropyl tris Ethoxysilane NMP solution 3.09g and BCS 13.7g were stirred with a magnetic stirrer for 2 hours to obtain a polyamic acid solution (B-3). (Synthesis Example 4) In a 200mL four-neck flask with a stirring device and a nitrogen introduction tube, put 3.18g (8.00mmol) of DA-3, 2.38g (6.00mmol) of DA-9, 1.79g (6.00 mmol) of DA-10 was added with 66.2 g of NMP, stirred and dissolved while feeding nitrogen. While stirring this diamine solution under water cooling, 4.25 g (19.5 mmol) of CA-4 was added, and 18.9 g of NMP was added, and stirred at 50° C. for 15 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The viscosity of the polyamic acid solution at 25°C was 264mPa･s. In a 100mL Erlenmeyer flask equipped with a stirrer, put 15.3 g of the polyamic acid solution, add 0.300 g of NMP, 10.3 g of GBL, and 1% by mass of 3-glycidoxypropyl tris Ethoxysilane NMP solution 1.54g and BCS 6.86g were stirred with a magnetic stirrer for 2 hours to obtain a polyamic acid solution (B-4). (Example 3) In a 50mL Erlenmeyer flask equipped with a stirring bar, 5.42 g of the solution (A-1) of the polyamic acid obtained in Example 1 and the polyamic acid obtained in Synthesis Example 1 were added The liquid crystal alignment agent (A-3) was obtained after 5.41 g of the solution (B-1) was stirred with a magnetic stirrer for 2 hours. (Example 4) In the 50mL Erlenmeyer flask equipped with a stirring bar, add 5.50 g of the polyimide solution (A-2) obtained in Example 2, and the polyimide obtained in Synthesis Example 2 The liquid crystal alignment agent (A-4) was obtained after 5.51 g of the solution (B-2) was stirred with a magnetic stirrer for 2 hours. (Example 5) In a 50mL Erlenmeyer flask equipped with a stirring bar, add 5.42 g of the polyamic acid solution (B-1) obtained in Synthesis Example 1, and the polyamic acid obtained in Synthesis Example 3 The liquid crystal alignment agent (A-5) was obtained after 5.42 g of the solution (B-3) was stirred with a magnetic stirrer for 2 hours. (Example 6) In a 50mL Erlenmeyer flask equipped with a stirring bar, 5.62 g of the solution (A-1) of the polyamic acid obtained in Example 1 and the polyamic acid obtained in Synthesis Example 4 were added The liquid crystal alignment agent (A-6) was obtained after 5.62 g of the solution (B-4) was stirred with a magnetic stirrer for 2 hours. <Evaluation of Sealing Adhesion> The liquid crystal alignment agent obtained in the examples and synthesis examples was filtered through a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and placed on a heating plate at 80°C After drying for 2 minutes, it baked at 230 degreeC for 20 minutes, and obtained the coating film with a film thickness of 100 nm. Two substrates obtained in this way were prepared, and a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was dropped after spreading a 4 μm bead spacer on the liquid crystal alignment film surface of one substrate. Next, with the liquid crystal alignment film surface of the other substrate being the inside, they were bonded so that the overlapping width of the substrates was 1 cm. At this time, adjust the dripping amount of the sealant until the diameter of the bonded sealant is about 3 mm. After fixing the bonded two substrates with a jig, heat curing was performed at 120°C for 1 hour, and a sample for adhesion evaluation was produced. Next, with the table-shaped precision universal testing machine AGS-X 500N of the Shimadzu Corporation system, after fixing the end parts of the upper and lower substrates, the sample made is pushed in from the upper part of the central part of the substrate, and the force (N ) was evaluated as the sealing adhesion. (Examples 7-12) After each of the liquid crystal alignment agents (A-1)-(A-6) obtained in Examples 1-6 is filtered with a filter of 1.0 μm, adhesiveness is produced as described above The evaluation samples were used to evaluate the sealing adhesion, and the results are shown in Table 4. (Comparative Examples 1~4) After filtering the liquid crystal alignment agents (B-1)~(B-4) obtained in Synthesis Examples 1~4 each with a filter of 1.0 μm, adhesiveness was produced as described above Table 4 shows the results of evaluating the sealing adhesive force of the evaluation samples. [0146]

[0147] When using the liquid crystal alignment agent described in the examples, a high seal adhesion force indicates good. (Example 13) In a 200mL four-neck flask with a stirring device and a nitrogen introduction tube, add 4.30g (17.6mmol) of DA-1, 2.67g (4.80mmol) of DA-2, and 3.27g (9.57 mmol) of DA-4 was added with 75.1 g of NMP, stirred and dissolved while feeding nitrogen. While stirring this diamine solution under water cooling, 4.66 g (20.7 mmol) of CA-1 was added, NMP 9.34 g was further added, and it stirred at 40 degreeC in nitrogen atmosphere for 3 hours. Furthermore, CA-2 1.78g (9.08mmol) was added, NMP 8.00g was added further, it stirred at 23 degreeC for 4 hours under nitrogen atmosphere, and obtained the solution of the polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25°C is 304mPa･s. In the 500mL Erlenmeyer flask with stirring bar, put into the solution 90.0g of this polyamic acid, add NMP 79.0g, acetic anhydride 7.92g, pyridine 2.04g, carry out after 30 minutes stirring at room temperature , and reacted at 55°C for 3 hours. This reaction solution was poured into 700 g of methanol, and the obtained precipitate was filtered. After the precipitate was washed with methanol, it was dried under reduced pressure at a temperature of 60° C. to obtain a polyimide powder. The imidization rate of this polyimide powder was 70%. [0150] In a 200mL Erlenmeyer flask equipped with a stirrer, 6.07g of the polyimide powder and 44.5g of NMP were added, and stirred at 50°C for 20 hours to dissolve it. Put 20.3 g of this solution in a 200 mL Erlenmeyer flask with a stirring bar, add 4.37 g of NMP, 16.2 g of GBL, and 2.43 g of an NMP solution containing 1% by mass of 3-glycidoxypropyltriethoxysilane And BCS 10.8g, after stirring with a magnetic stirrer for 2 hours, a polyimide solution (A-7) was obtained. (Example 14) In a 200mL four-neck flask with a stirring device and a nitrogen introduction tube, add 4.30g (17.6mmol) of DA-1, 2.67g (4.80mmol) of DA-2, and 1.91g (4.80 mmol) of DA-3, 1.64 g (4.80 mmol) of DA-4, and 77.1 g of NMP were stirred and dissolved while feeding nitrogen. 4.66 g (20.7 mmol) of CA-1 was added, stirring this diamine solution under water cooling, and 8.88 g of NMP was added, and it stirred at 40 degreeC in nitrogen atmosphere for 3 hours. And 1.71g (8.69mmol) of CA-2 was added, NMP8.00g was added further, it stirred at 23 degreeC under nitrogen atmosphere for 4 hours, and the solution of the polyamic acid was obtained. The viscosity of the polyamic acid solution at a temperature of 25 is 312mPa･s. In the 500mL Erlenmeyer flask with a stirring bar, add the solution 90.0g of this polyamic acid, add NMP 79.0g, acetic anhydride 7.02g, pyridine 1.81g, after stirring at room temperature for 30 minutes, The reaction was carried out at 55°C for 3 hours. This reaction solution was poured into 700 g of methanol, and the obtained precipitate was filtered. After the precipitate was washed with methanol, it was dried under reduced pressure at a temperature of 60° C. to obtain a polyimide powder. The imidization rate of this polyimide powder was 71%. [0153] In a 200 mL Erlenmeyer flask equipped with a stirrer, 6.03 g of the polyimide powder was placed, 44.2 g of NMP was added, and stirred at 50° C. for 20 hours to dissolve it. Put 21.0 g of this solution into a 200 mL Erlenmeyer flask with a stirring bar, add 4.48 g of NMP, 16.8 g of GBL, and 2.52 g of NMP solution containing 1% by mass of 3-glycidoxypropyltriethoxysilane. g and 11.2 g of BCS were stirred with a magnetic stirrer for 2 hours to obtain a polyimide solution (A-8). (Synthesis Example 5) In a 1L four-necked flask with a stirring device and a nitrogen introduction tube, put 4.30g (17.6mmol) of DA-1, 5.73g (14.3mmol) of DA-3, NMP 73.6 g, stirring and dissolving while feeding nitrogen. While stirring this diamine solution under water cooling, 4.66 g (20.7 mmol) of CA-1 was added, NMP 9.69 g was added further, and it stirred at 40 degreeC in nitrogen atmosphere for 3 hours. Furthermore, 1.50 g (7.65 mmol) of CA-2 was added, and 8.53 g of NMP was added, and stirred at 23° C. for 4 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 is 290mPa･s. In the 500mL Erlenmeyer flask with stirring bar, put into the solution 90.0g of this polyamic acid, add NMP 79.0g, acetic anhydride 8.16g, pyridine 2.10g, carry out after stirring for 30 minutes at room temperature , and reacted at 55°C for 3 hours. This reaction solution was poured into 700 g of methanol, and the obtained precipitate was filtered. After the precipitate was washed with methanol, it was dried under reduced pressure at a temperature of 60° C. to obtain a polyimide powder. The imidization rate of this polyimide powder was 72%. 6.10 g of the polyimide powder was placed in a 200 mL Erlenmeyer flask equipped with a stirring bar, and 44.7 g of NMP was added thereto, and stirred at 50° C. for 20 hours to dissolve it. Then put 25.0 g of this solution in a 200 mL Erlenmeyer flask with a stirring bar, add 4.90 g of NMP, 19.8 g of GBL, and 3.00 g of NMP solution containing 1% by mass of 3-glycidoxypropyltriethoxysilane and 13.3 g of BCS was stirred with a magnetic stirrer for 2 hours to obtain a polyimide solution (B-5). [0157] <Evaluation of Liquid Crystal Alignment> The following shows the production method of the liquid crystal cell to evaluate the liquid crystal alignment. [0158] A liquid crystal cell having a configuration of a liquid crystal display element of the FFS method was produced. First prepare the substrate with electrodes attached. The size of the substrate is 30mm×35mm, and the glass substrate is 0.7mm thick. On the substrate as the first layer, the IZO electrode constituting the counter electrode is formed on the entire surface. On the counter electrode of the first layer, as a second layer, a deposited SiN (silicon nitride) film is formed by the CVD method. The SiN film of the second layer has a film thickness of 100 nm and functions as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning the IZO film as the third layer is arranged to form two pixels of a first pixel and a second pixel. The size of each pixel is about 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 form an electrical insulator through the function of the SiN film of the second layer. [0159] The pixel electrode of the third layer is formed by arranging plural numbers of electrode elements bent in the shape of "く" at the center, and has a comb-like shape. The width in the lateral direction of each electrode element was 3 μm, and the interval between electrode elements was 6 μm. The pixel electrode forming each pixel is composed of plural arrays of electrode elements in the shape of "く" with a curved central part. Therefore, the shape of each pixel is not a rectangular shape, and the central part is curved in bold letters like the electrode elements. Like the shape of the word く. Each pixel is divided into upper and lower parts by using the central curved portion as a boundary, and has a first area above the curved portion and a second area below the curved portion. [0160] When comparing the first region and the second region of each pixel, the formation directions of the electrode elements constituting these pixel electrodes are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, in the first area of the pixel, the electrode elements of the pixel electrode form an angle of +10° (clockwise), and in the second area of the pixel, the The electrode elements of the prime electrode form an angle of -10° (clockwise). That is, in the first area and the second area of each pixel, the rotation action (in-plane switching) of the liquid crystal in the substrate plane caused by the input voltage between the pixel electrode and the counter electrode The directions are opposite to each other. [0161] Next, after filtering the liquid crystal alignment agent obtained in the examples and synthesis examples with a 1.0 μm filter, it was coated by spin coating on the prepared substrate with the above-mentioned electrodes. After drying for 2 minutes on a hot plate at 80° C., firing was performed for 20 minutes in a hot air circulation oven at 230° C. to obtain a polyimide film with a film thickness of 60 nm. The polyimide film was rubbed with rayon cloth (roller diameter: 120mm, roll rotation speed: 500rpm, moving speed: 30mm/sec, pushing length: 0.3mm, rubbing direction: against the third layer IZO comb electrode After 10° inclined direction), ultrasonic irradiation was performed in pure water for 1 minute, followed by washing, and water droplets were removed by blowing air. Thereafter, it was dried at 80° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film. Also, as the opposite substrate, ITO electrodes were formed on the backside, and the polyimide film was formed on the glass substrate with columnar spacers with a height of 4 μm in the same manner as above, so that the alignment treatment was performed under the same procedure as above. Substrate with liquid crystal alignment film. These 2 substrates with liquid crystal alignment film were used as a group, and the sealant was printed with the liquid crystal injection port remaining on the substrate, and the other substrate faced the liquid crystal alignment film surface, and the rubbing direction was antiparallel. Thereafter, the sealant was hardened to produce a hollow cell with a cell gap of 4 μm. Liquid crystal MLC-3019 (manufactured by Merck & Co.) was injected into the ghost cells by a reduced-pressure injection method, and the injection port was sealed to obtain a liquid crystal cell of the FFS system. Thereafter, the obtained liquid crystal unit was heated at 120° C. for 1 hour, and left overnight at 23° C. for evaluation of liquid crystal alignment. [0162] Using this liquid crystal cell, under a constant temperature environment of 60° C., an AC voltage of 9 VPP with a frequency of 30 Hz was input for 190 hours. Thereafter, a short-circuit phenomenon was formed between the pixel electrode and the counter electrode of the liquid crystal cell, and it was left at room temperature for one day. After placement, the liquid crystal cell is arranged between two polarizers whose polarizing axes are perpendicular to each other, and the backlight is turned on without input voltage, and the configuration angle of the liquid crystal cell is adjusted so that the brightness of the transmitted light is minimum. On the other hand, the rotation angle when the liquid crystal cell is rotated from the angle at which the second area of the first pixel becomes darkest to the angle at which the first area becomes darkest is calculated as angle Δ. Likewise for the second pixel, the second area is compared with the first area to calculate the same angle Δ. And the average value of the angle Δ values of the first pixel and the second pixel was calculated as the angle Δ of the liquid crystal cell. That is, the smaller the angle, the better the liquid crystal alignment. (Examples 15-18) The liquid crystal alignment agents (A-2), (A-4), (A-7) and (A-8) obtained in Examples 2, 4, 13, and 14 were respectively After filtering with a filter of 1.0 μm, the adhesive evaluation sample described above was produced, and the seal adhesive force was evaluated. The results and the results of the angle Δ of the above-mentioned liquid crystal cell are shown in Table 5. (Comparative Example 5) After filtering the liquid crystal alignment agent (B-5) obtained in Synthesis Example 5 with a filter of 1.0 μm, as described above, a sample for adhesiveness evaluation was produced to evaluate the result of sealing adhesive force And the results of the angle Δ of the above-mentioned liquid crystal cell are shown in Table 5. [0166]

[0167] When using the liquid crystal alignment agent described in the examples, its sealing strength is high, and the angle Δ of the aged liquid crystal cell is small, and its liquid crystal alignment is also good. [Industrial Applicability] [0168] The liquid crystal alignment agent of the present invention solves the problem of insufficient display near the frontal margin by improving the adhesion between the sealant and the liquid crystal alignment film for narrow frontal margin liquid crystal display elements that can ensure a large number of display surfaces. Both are industrially useful.

Claims (6)

A liquid crystal alignment agent, which is characterized by containing the following polymer, which is at least one kind of polyimide selected from the following imides of polyamic acid and whose imidization rate is 70% or more. The polyamic acid is a diamine component containing at least one diamine selected from the following component (A) and the following component (B) and a diamine having a skeleton of the following component (C) and a tetracarboxylic dianhydride The reactant; (A) component: a diamine having at least one structure selected from the following formula (1-1) and the following formula (1-2)

(In the formula, D represents a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring with a divalent carbon number of 1 to 20, D represents a variety of substituents, and E represents a single bond or a saturated hydrocarbon group with a divalent carbon number of 1 to 20. Hydrocarbon group, unsaturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic ring, F represents a single bond or ether bond (-O-), ester bond (-OCO-, -COO-), m represents 1 or 0, R represents a thermal detachment group, * represents the bonding with other atoms); (B) component: diamine having the structure of the following formula (2)

(wherein, X ₁ represents at least one divalent organic group selected from the group consisting of -O-, -NQ ¹ -, -CONQ ¹ -, -NQ ¹ CO-, -CH ₂ O-, and -OCO-, Q ¹ represents a hydrogen atom or an alkyl group selected from 1 to 3 carbons, X ₂ represents a single bond or at least one group selected from aliphatic hydrocarbon groups with 1 to 20 carbons, non-aromatic cyclic hydrocarbon groups and aromatic hydrocarbon groups. A divalent organic group, X ₃ represents a single bond or is selected from -O-, -NQ ² -, -CONQ ² -, -NQ ² CO-, -COO-, -OCO- and -O(CH ₂ ) _m -(m is an integer from 1 to 5) grouped with at least one divalent organic group, Q ² represents a hydrogen atom or an alkyl group with 1 to 3 carbons, X ₄ represents an aromatic heterocyclic ring, * represents a combination with other atoms bond); (C) component: diamine having at least one structure selected from the following formula (a) and the following formula (b)

(In the formula, X ¹ is an oxygen atom or a sulfur atom, A ¹ to A ³ are each independently a hydrogen atom or a hydrocarbon group with a carbon number of 1 to 3, and the total number of carbons is 1 to 9; and, * represents a bond with other atoms Knot). A liquid crystal alignment film is characterized by containing the following polymers, the polymer The substance is obtained from the liquid crystal alignment agent as claimed in claim 1, and has an aromatic heterocycle, primary amine group and secondary amine group in the structure. The liquid crystal alignment film according to claim 2, which is a film formed by firing, wherein the skeleton of the aromatic heterocycle, the primary amine group, and the secondary amine group are contained in a structure formed by firing the middle one. The liquid crystal alignment film according to claim 2 or claim 3, wherein the aromatic heterocycle is a pyridine skeleton, a benzimidazole skeleton or an imidazole skeleton. The liquid crystal alignment film according to claim 3, wherein the fired product is produced at a firing temperature of 100°C to 300°C. A liquid crystal display element, characterized by comprising the liquid crystal alignment film according to any one of claim 2 to claim 5.