TWI513736B - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, polymer and compound - Google Patents

Description

液晶配向劑、液晶配向膜、液晶顯示元件、聚合物及化合物Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer and compound

本發明涉及一種液晶配向劑、液晶配向膜、液晶顯示元件、聚合物及化合物。詳細而言涉及一種可使液晶配向膜的耐侯性良好的液晶配向劑、以及使用該液晶配向劑而製作的液晶配向膜及液晶顯示元件等。The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, a polymer, and a compound. More specifically, the present invention relates to a liquid crystal alignment agent which is excellent in weather resistance of a liquid crystal alignment film, and a liquid crystal alignment film and a liquid crystal display element which are produced by using the liquid crystal alignment agent.

於先前，作為液晶顯示元件，開發了電極結構或所使用的液晶分子的物性等不同的各種驅動方式的液晶顯示元件，例如已知有扭轉向列(Twisted Nematic，TN)型或超扭轉向列(Super Twisted Nematic，STN)型、垂直配向(Vertical Alignment，VA)型、共面切換(In Plane Switching，IPS)型、邊緣場切換(Fringe Field Switching，FFS)型、光學補償彎曲型(Optically Compensated Bend，OCB)型等液晶顯示元件。該些液晶顯示元件包含用以使液晶分子配向的液晶配向膜。自耐熱性、機械強度、與液晶的親和性等各種特性良好的方面考慮，一般情況下使用聚醯胺酸或聚醯亞胺作為液晶配向膜的材料。Conventionally, liquid crystal display elements of various driving methods having different electrode structures or physical properties of liquid crystal molecules to be used have been developed as liquid crystal display elements. For example, a twisted nematic (TN) type or a super twisted nematic is known. (Super Twisted Nematic, STN) type, Vertical Alignment (VA) type, In Plane Switching (IPS) type, Fringe Field Switching (FFS) type, Optically compensated bending type (Optically Compensated) Liquid crystal display elements such as Bend, OCB). The liquid crystal display elements include a liquid crystal alignment film for aligning liquid crystal molecules. In view of various characteristics such as heat resistance, mechanical strength, and affinity with liquid crystal, polyphthalic acid or polyimine is generally used as a material of the liquid crystal alignment film.

而且，於近年來，液晶顯示元件不僅如先前那樣在個人電腦等的顯示終端中使用，而且在例如液晶電視或汽車導航系統、手機、智能手機、信息顯示器等多種用途中使用。隨著此種多用途化，於液晶顯示元件中要求顯示品質的更進一步高品質化，驅動方式或元件結構的改良、以及作為液晶顯示元件的構成構件之一的液晶配向膜的改良不 斷發展。例如，作為液晶顯示元件的重要特性，可列舉耐侯性良好，具體而言要求即使在長時間驅動或暴露於光應力的情況下亦可良好地維持電氣特性(耐光性良好)、或者即使在高溫高濕下亦可良好地維持電氣特性(耐高溫高濕性良好)。Further, in recent years, liquid crystal display elements have been used not only in display terminals such as personal computers as in the prior art, but also in various applications such as liquid crystal televisions or car navigation systems, mobile phones, smart phones, and information displays. With the versatility of the liquid crystal display device, it is required to further improve the quality of the display quality, improve the driving method or the device structure, and improve the liquid crystal alignment film which is one of the constituent members of the liquid crystal display device. Break development. For example, as an important characteristic of a liquid crystal display element, durability is good, and specifically, it is required to maintain electrical characteristics (good light resistance) well, or even at a high temperature, even when driving for a long time or exposure to light stress. Electrical properties can be maintained well under high humidity (high temperature and high humidity resistance).

因此，在先前提出了如下的方法：通過在聚醯亞胺類液晶配向膜中使醯亞胺化率提高，可使液晶顯示元件的耐候性提高。另一方面，在提高液晶配向膜的醯亞胺化率的情況下，液晶配向劑於基板中的印刷性降低，鑒於此現象而通過選擇各種液晶配向膜材料的成分來實現液晶顯示元件的耐候性的改善，提出了各種此種液晶配向膜材料(例如參照專利文獻1或專利文獻2)。Therefore, a method has been proposed in which the weather resistance of the liquid crystal display element can be improved by increasing the imidization ratio in the polyimine-based liquid crystal alignment film. On the other hand, when the sulfhydrylation ratio of the liquid crystal alignment film is increased, the printability of the liquid crystal alignment agent in the substrate is lowered, and in view of this phenomenon, the weather resistance of the liquid crystal display element is realized by selecting components of various liquid crystal alignment film materials. Various kinds of such liquid crystal alignment film materials have been proposed for improvement of properties (for example, refer to Patent Document 1 or Patent Document 2).

[先前技術文獻][Previous Technical Literature] [專利文獻][Patent Literature]

[專利文獻1]日本專利特開2010-2501號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-2501

[專利文獻2]日本專利特開2011-28223號公報[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-28223

對液晶顯示元件的高性能化的要求進一步提高，特別是於隨著其多用途化而在較先前更嚴酷的環境下使用的方面而言，要求即使暴露在熱或光等應力下的情況下，亦可良好地維持顯示品質。The demand for high performance of liquid crystal display elements is further improved, particularly in the case of being used in a more severe environment than in the prior art, insofar as it is exposed to stress such as heat or light. It can also maintain the display quality well.

本發明是鑑於上述課題而成的，主要目的在於提供一種可改善液晶配向膜的耐候性的液晶配向劑、以及使用該液晶配向劑所製作的液晶配向膜及液晶顯示元件。而且， 另一個目的在於提供一種可在液晶配向劑的調製中適宜使用的新穎的聚合物、及在該聚合物的合成中所使用的新穎的化合物。The present invention has been made in view of the above problems, and a main object thereof is to provide a liquid crystal alignment agent capable of improving weather resistance of a liquid crystal alignment film, and a liquid crystal alignment film and a liquid crystal display element produced by using the liquid crystal alignment agent. and, Another object is to provide a novel polymer which can be suitably used in the preparation of a liquid crystal alignment agent, and novel compounds which are used in the synthesis of the polymer.

本發明者等人為了達成如上所述的先前技術的課題而進行了銳意研究，結果發現藉由使用使四羧酸二酐與具有特定結構的二胺反應所得的聚合物作為液晶配向劑中所含有的聚合物成分可解決上述課題，從而完成本發明。具體而言，通過本發明而提供以下的液晶配向劑、液晶配向膜及液晶顯示元件，且提供適於在液晶配向劑的製造中使用的新穎的聚合物及化合物。The inventors of the present invention conducted intensive studies in order to achieve the problems of the prior art as described above, and as a result, found that a polymer obtained by reacting a tetracarboxylic dianhydride with a diamine having a specific structure is used as a liquid crystal alignment agent. The polymer component contained can solve the above problems, and the present invention has been completed. Specifically, the present invention provides the following liquid crystal alignment agents, liquid crystal alignment films, and liquid crystal display elements, and provides novel polymers and compounds suitable for use in the production of liquid crystal alignment agents.

本發明的一個方面是提供一種液晶配向劑，其含有選自由使四羧酸二酐與二胺反應而所得的聚醯胺酸及該聚醯胺酸進行脫水閉環而成的聚醯亞胺所構成的群組的至少一種聚合物，所述二胺包含下述式(A)所表示的化合物(a)， One aspect of the present invention provides a liquid crystal alignment agent comprising a polyimine which is selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine and a polycyclic hydrazine ring which is subjected to dehydration ring closure. At least one polymer of the group consisting of the compound (a) represented by the following formula (A),

(式(A)中，Am¹ 是與氮原子一同形成吡咯烷環、哌啶環或六亞甲基亞胺環的2價基，該些基的環部分上亦可鍵結取代基；其中，於Am¹ 中，構成環的氮原子鍵結於X² 上；X¹ 是單鍵、氧原子、羰基、*-COO-、*-OCO-、-NH-、 *-Ar¹ -O-、*-O-Ar¹ -、*-COO-Ar¹ -、或*-R³ -OCO-(其中，Ar¹ 是伸苯基或於伸苯基上鍵結有取代基的2價基，R³ 是碳數為1或2的烷二基(alkanediyl)；“*”表示與含氮雜環的鍵結的鍵)；X² 是單鍵或羰基；R¹ 是1價有機基，r分別獨立為0~4的整數；其中，於r的合計為2以上的情況下，多個R¹ 獨立地具有上述定義)。(In the formula (A), Am ¹ is a divalent group which forms a pyrrolidine ring, a piperidine ring or a hexamethyleneimine ring together with a nitrogen atom, and the ring moiety of the group may also bond a substituent; In Am ¹ , the nitrogen atom constituting the ring is bonded to X ² ; X ¹ is a single bond, an oxygen atom, a carbonyl group, *-COO-, *-OCO-, -NH-, *-Ar ¹ -O- , *-O-Ar ¹ -, *-COO-Ar ¹ -, or *-R ³ -OCO- (wherein Ar ¹ is a phenyl group or a divalent group having a substituent bonded to a phenyl group, R ³ is an alkanediyl having a carbon number of 1 or 2; "*" represents a bond to a nitrogen-containing heterocyclic ring; X ² is a single bond or a carbonyl group; and R ¹ is a monovalent organic group, r Each of them is independently an integer of 0 to 4; wherein, when the total of r is 2 or more, a plurality of R ¹ independently have the above definition).

本發明的液晶配向劑包含於主鏈上具有自上述式(A)所表示的化合物中的2個一級胺基分別除去1個氫原子的結構(以下亦稱為“特定結構”)的聚醯胺酸及其醯亞胺化聚合物的至少1種作為聚合物成分。利用此種液晶配向劑可製造耐光性及耐高溫高濕性優異的液晶配向膜。The liquid crystal alignment agent of the present invention comprises a polyfluorene having a structure in which one hydrogen atom is removed from two primary amino groups in the compound represented by the above formula (A) (hereinafter also referred to as "specific structure"). At least one of the amine acid and its quinone imidized polymer is used as a polymer component. A liquid crystal alignment film excellent in light resistance and high temperature and high humidity resistance can be produced by using such a liquid crystal alignment agent.

而且，存在如下現象：在液晶配向膜的製造步驟中，在使用液晶配向劑而形成於基板上的塗膜上產生針孔或塗膜不均等缺陷。在這種情況下，有時自基板上剝離塗膜而再利用基板，在此種再加工中，要求塗膜相對於基板的剝離性良好。於這一方面而言，利用本發明的液晶配向劑可獲得再加工(re-work)性良好的液晶配向膜。而且，利用本發明的液晶配向劑而形成的液晶配向膜的印刷性亦良好。Further, in the production step of the liquid crystal alignment film, defects such as pinholes or uneven coating film are generated on the coating film formed on the substrate by using the liquid crystal alignment agent. In this case, the coating film may be peeled off from the substrate to reuse the substrate, and in such reworking, the peeling property of the coating film with respect to the substrate is required to be good. In this respect, a liquid crystal alignment film having good re-workability can be obtained by using the liquid crystal alignment agent of the present invention. Further, the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is also excellent in printability.

在本發明中，上述化合物(a)優選以下述式(A-1)而表示。In the present invention, the above compound (a) is preferably represented by the following formula (A-1).

[化2] [Chemical 2]

(式(A-1)中，X¹ 是單鍵、氧原子、羰基、*-COO-、*-OCO-、-NH-、*-Ar¹ -O-、*-O-Ar¹ -、*-COO-Ar¹ -、或*-R³ -OCO-(其中，Ar¹ 是伸苯基或於伸苯基上鍵結有取代基的2價基，R³ 是碳數為1或2的烷二基；“*”表示與含氮雜環的鍵結的鍵)；X² 是單鍵或羰基；R¹ 及R⁴ 分別獨立為1價有機基，r及s分別獨立為0~4的整數；其中，於r的合計為2以上的情況下，多個R¹ 獨立地具有上述定義，於s為2以上的情況下，多個R⁴ 獨立地具有上述定義)。(In the formula (A-1), X ¹ is a single bond, an oxygen atom, a carbonyl group, *-COO-, *-OCO-, -NH-, *-Ar ¹ -O-, *-O-Ar ¹ -, *-COO-Ar ¹ -, or *-R ³ -OCO- (wherein Ar ¹ is a phenyl group or a divalent group having a substituent bonded to a phenyl group, and R ³ is a carbon number of 1 or 2 An alkanediyl group; "*" represents a bond to a nitrogen-containing heterocyclic ring; X ² is a single bond or a carbonyl group; R ¹ and R ⁴ are each independently a monovalent organic group, and r and s are each independently 0~ An integer of 4; wherein, when the total of r is 2 or more, a plurality of R ¹ independently have the above definition, and when s is 2 or more, a plurality of R ⁴ independently have the above definition).

在本發明中，上述X² 優選為單鍵，上述X¹ 優選為*-COO-、*-OCO-、-NH-或*-R³ -OCO-(其中，R³ 是碳數為1或2的烷二基)。而且，上述聚合物的合成中所使用的四羧酸二酐優選包含選自由2,3,5-三羧基環戊基乙酸二酐及1,2,3,4-環丁烷四羧酸二酐所構成的群組中的至少一種。In the present invention, the above X ² is preferably a single bond, and the above X ¹ is preferably *-COO-, *-OCO-, -NH- or *-R ³ -OCO- (wherein R ³ is a carbon number of 1 or 2 alkanediyl). Further, the tetracarboxylic dianhydride used in the synthesis of the above polymer preferably contains a solvent selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,2,3,4-cyclobutanetetracarboxylic acid At least one of the group consisting of anhydrides.

本發明在一個方面中提供一種利用上述所記載的液晶配向劑而形成的液晶配向膜。另外，本發明在另一方面中提供一種包含上述液晶配向膜的液晶顯示元件。In one aspect, the present invention provides a liquid crystal alignment film formed using the liquid crystal alignment agent described above. Further, the present invention provides, in another aspect, a liquid crystal display element comprising the above liquid crystal alignment film.

本發明在另一方面中提供一種使包含上述式(A)所表示的化合物(a)的二胺與四羧酸二酐反應所得的聚合物。而且，提供一種上述式(A)所表示的化合物。In another aspect, the present invention provides a polymer obtained by reacting a diamine comprising the compound (a) represented by the above formula (A) with a tetracarboxylic dianhydride. Further, a compound represented by the above formula (A) is provided.

本發明的液晶配向劑含有選自由使四羧酸二酐與二胺反應而所得的聚醯胺酸及該聚醯胺酸進行脫水閉環而成的聚醯亞胺所構成的群組的至少一種聚合物。以下，對本發明的液晶配向劑加以詳細說明。The liquid crystal alignment agent of the present invention contains at least one selected from the group consisting of polylysine obtained by reacting tetracarboxylic dianhydride with a diamine and polyimine which is obtained by dehydration ring closure of the polyamic acid. polymer. Hereinafter, the liquid crystal alignment agent of the present invention will be described in detail.

<聚醯胺酸><polylysine> [四羧酸二酐][tetracarboxylic dianhydride]

用以合成本發明中的聚醯胺酸的四羧酸二酐例如可列舉脂肪族四羧酸二酐、脂環族四羧酸二酐、芳香族四羧酸二酐等。作為該些化合物的具體例，脂肪族四羧酸二酐例如可列舉丁烷四羧酸二酐等；脂環族四羧酸二酐例如可列舉1,2,3,4-環丁烷四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘並[1,2-c]呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘並[1,2-c]呋喃-1,3-二酮、3-氧雜二環[3.2.1]辛烷-2,4-二酮-6-螺-3'-(四氫呋喃-2',5'-二酮)、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、3,5,6-三羧基-2-羧基甲基降冰片烷-2：3,5：6-二酐、2,4,6,8-四羧基雙環[3.3.0]辛烷-2：4,6：8-二酐、4,9-二氧雜三環[5.3.1.0^2,6 ]十一烷-3,5,8,10-四酮、環己烷四羧酸二酐等；芳香族四羧酸二酐例如可列舉均苯四羧酸二酐等；除此以外亦可使用日本專利特開2010-97188號公報中所記載的四羧酸二酐。Examples of the tetracarboxylic dianhydride for synthesizing the polyamic acid in the present invention include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the compounds include aliphatic butane tetracarboxylic dianhydride, and butane tetracarboxylic dianhydride. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutane IV. Carboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2 ,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-di Keto-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane Alkene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] Octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraketone Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like; and the fourth described in JP-A-2010-97188 can also be used. Carboxylic dianhydride.

另外，聚醯胺酸的合成中所使用的四羧酸二酐可單獨使用1種或者將2種以上組合使用。In addition, the tetracarboxylic dianhydride used for the synthesis of the poly-proline may be used singly or in combination of two or more.

用以合成聚醯胺酸的四羧酸二酐優選包含該些四羧酸二酐中的脂環族四羧酸二酐。更優選包含選自由2,3,5-三羧基環戊基乙酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘並[1,2-c]呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二氧代-3-呋喃基)-萘並[1,2-c]呋喃-1,3-二酮、2,4,6,8-四羧基雙環[3.3.0]辛烷-2：4,6：8-二酐及1,2,3,4-環丁烷四羧酸二酐所構成的群組的至少一種，特別優選包含2,3,5-三羧基環戊基乙酸二酐及1,2,3,4-環丁烷四羧酸二酐的至少任意者(特定四羧酸二酐)。而且，優選包含相對於聚醯胺酸的合成中所使用的四羧酸二酐的總量而言為10 mol%以上的該特定四羧酸二酐，更優選包含20 mol%~100 mol%，特別優選包含50 mol%~100 mol%。The tetracarboxylic dianhydride used to synthesize the polyamic acid preferably contains the alicyclic tetracarboxylic dianhydride in the tetracarboxylic dianhydride. More preferably, it comprises a compound selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3 -furyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2 ,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane- At least one of the group consisting of 2:4,6:8-dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride, particularly preferably comprising 2,3,5-tricarboxycyclopentyl At least one of acetic acid dianhydride and 1,2,3,4-cyclobutane tetracarboxylic dianhydride (specific tetracarboxylic dianhydride). Further, it is preferable that the specific tetracarboxylic dianhydride is contained in an amount of 10 mol% or more based on the total amount of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid, and more preferably from 20 mol% to 100 mol%. It is particularly preferable to contain 50 mol% to 100 mol%.

另外，上述四羧酸二酐就如下方面而言均具有同樣的作用：藉由與下述式(A)所表示的化合物(a)的聚合反應而可獲得能夠形成耐光性及耐高溫高濕性優異的液晶配向膜的聚醯胺酸的方面。因此，即使是以下的實例中未記載的四羧酸二酐，亦可於本發明中使用。Further, the above tetracarboxylic dianhydride has the same effect as follows: by the polymerization reaction with the compound (a) represented by the following formula (A), it is possible to obtain light resistance and high temperature and high humidity resistance. The aspect of polylysine which is excellent in liquid crystal alignment film. Therefore, even a tetracarboxylic dianhydride which is not described in the following examples can be used in the present invention.

[二胺][diamine] 《化合物(a)》Compound (a)

用以合成本發明中的聚醯胺酸的二胺包含下述式(A)所表示的化合物(a)。The diamine used for the synthesis of the poly-proline in the present invention contains the compound (a) represented by the following formula (A).

[化3] [Chemical 3]

式(A)中，Am¹ 是與氮原子一同形成吡咯烷環、哌啶環或六亞甲基亞胺環的2價基，該些基的環部分上亦可鍵結取代基。其中，於Am¹ 中，構成環的氮原子鍵結於X² 上。X¹ 是單鍵、氧原子、羰基、*-COO-、*-OCO-、-NH-、*-Ar¹ -O-、*-O-Ar¹ -、*-COO-Ar¹ -、或*-R³ -OCO-(其中，Ar¹ 是伸苯基或於伸苯基上鍵結有取代基的2價基，R³ 是碳數為1或2的烷二基。“*”表示與含氮雜環的鍵結的鍵)。X² 是單鍵或羰基。R¹ 是1價有機基，r分別獨立為0~4的整數。其中，於r的合計為2以上的情況下，多個R¹ 獨立地具有上述定義。In the formula (A), Am ¹ is a divalent group which forms a pyrrolidine ring, a piperidine ring or a hexamethyleneimine ring together with a nitrogen atom, and a substituent may be bonded to the ring portion of the group. Among them, in Am ¹ , the nitrogen atom constituting the ring is bonded to X ² . X ¹ is a single bond, an oxygen atom, a carbonyl group, *-COO-, *-OCO-, -NH-, *-Ar ¹ -O-, *-O-Ar ¹ -, *-COO-Ar ¹ -, or *-R ³ -OCO- (wherein Ar ¹ is a phenyl group or a divalent group having a substituent bonded to a phenyl group, and R ³ is an alkanediyl group having a carbon number of 1 or 2. "*" indicates a bond with a nitrogen-containing heterocyclic ring). X ² is a single bond or a carbonyl group. R ¹ is a monovalent organic group, and r is independently an integer of 0 to 4. However, when the total of r is 2 or more, a plurality of R ¹ independently have the above definition.

關於式(A)，Am¹ 是與氮原子一同形成吡咯烷環、哌啶環或六亞甲基亞胺環的2價基，構成該些環(含氮雜環)的氮原子經由2價基“X² ”而鍵結於其中一個胺基苯基上，碳原子經由2價基“X¹ ”而鍵結於另一個胺基苯基上。含氮雜環亦可具有取代基，該取代基例如可列舉碳數為1~10的烷基、碳數為3~12的脂環族烴基、碳數為6~12的芳香族烴基、羥基、鹵素原子(氟原子、氯原子、溴原子、碘原子等)、硝基、氰基等。而且，該取代基亦可為於上述所例示的烴基的碳-碳鍵間具有例如-O-、-CO-、-COO-、-OCO-等的1價基，該烴基所具有的氫原子的至 少一部分亦可被鹵素原子等取代。With respect to formula (A), Am ¹ is a divalent group which forms a pyrrolidine ring, a piperidine ring or a hexamethyleneimine ring together with a nitrogen atom, and the nitrogen atom constituting the ring (nitrogen-containing hetero ring) is via a divalent group. The group "X ² " is bonded to one of the aminophenyl groups, and the carbon atom is bonded to the other aminophenyl group via the divalent group "X ¹ ". The nitrogen-containing hetero ring may have a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a hydroxyl group. A halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a nitro group, a cyano group or the like. Further, the substituent may have a monovalent group such as -O-, -CO-, -COO-, -OCO- or the like between the carbon-carbon bonds of the above-exemplified hydrocarbon groups, and the hydrogen atom of the hydrocarbon group At least a part of it may be substituted by a halogen atom or the like.

此處，碳數為1~10的烷基例如可列舉甲基、乙基、正丙基、異丙基、正丁基、2-丁基、異丁基、第三丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基等；碳數為3~12的脂環族烴基例如可列舉環戊基、環己基等；碳數為6~12的芳香族烴基例如可列舉苯基、甲苯基、苄基等。Here, examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-butyl group, isobutyl group, tert-butyl group, and n-pentyl group. , n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, and the like; examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, and the like; and a carbon number of 6 to 12; Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, and a benzyl group.

由Am¹ 與氮原子所形成的含氮雜環特別優選為哌啶環。亦即，化合物(a)優選為下述式(A-1)所表示的二胺。The nitrogen-containing heterocyclic ring formed of Am ¹ and a nitrogen atom is particularly preferably a piperidine ring. In other words, the compound (a) is preferably a diamine represented by the following formula (A-1).

式(A-1)中，R⁴ 是1價有機基，s是0~4的整數。其中，於s為2以上的情況下，多個R⁴ 獨立地具有上述定義。R¹ 、X¹ 、X² 及r與上述式(A)相同。In the formula (A-1), R ⁴ is a monovalent organic group, and s is an integer of 0 to 4. However, when s is 2 or more, a plurality of R ⁴ independently have the above definition. R ¹ , X ¹ , X ² and r are the same as the above formula (A).

上述式(A-1)中的R⁴ 是1價有機基，其具體例可列舉在Am¹ 的說明中作為含氮雜環亦可具有的取代基而例示的基。另外，於苯環上鍵結有多個R⁴ 的情況下，該些多個R⁴ 可相同亦可不同。R ⁴ in the above formula (A-1) is a monovalent organic group, and specific examples thereof include those exemplified as a substituent which the nitrogen-containing hetero ring may have in the description of Am ¹ . Further, when a plurality of R ⁴ are bonded to the benzene ring, the plurality of R ⁴ may be the same or different.

關於式(A)及式(A-1)的X¹ ，*-Ar¹ -O-、*-O-Ar¹ -、及*-COO-Ar¹ -中的Ar¹ 是伸苯基或於伸苯基上鍵結有取代基的2價基。該取代基例如可列舉在Am¹ 的說明中作為含氮雜環亦可具有的取代基而例示的基。X on the formula (A) and of formula (A-1) is ^{1, * - Ar 1 -O -} , * - O-Ar 1 -, and * -COO-Ar ¹ - Ar ¹ is phenylene or to A divalent group having a substituent bonded to a phenyl group. The substituent is exemplified as a substituent which may be a nitrogen-containing heterocyclic ring in the description of Am ¹ .

作為X¹ ，其中優選為*-COO-、*-OCO-、-NH-或*-R³ -OCO-，更優選為*-COO-、*-OCO-或-NH-。該些X¹ 的鍵結位置並無特別限定，優選相對於含氮雜環的氮原子而言為3位或4位，更優選為4位。As X ¹ , preferred is *-COO-, *-OCO-, -NH- or *-R ³ -OCO-, more preferably *-COO-, *-OCO- or -NH-. The bonding position of these X ¹ is not particularly limited, but is preferably 3 or 4 positions, more preferably 4 positions, with respect to the nitrogen atom of the nitrogen-containing hetero ring.

X² 為單鍵或羰基，優選為單鍵。X ² is a single bond or a carbonyl group, preferably a single bond.

R¹ 是1價有機基，其具體例可列舉在Am¹ 的說明中作為含氮雜環亦可具有的取代基而例示的基。另外，在式中存在多個R¹ 的情況下，該些多個R¹ 可相互相同亦可不同。R ¹ is a monovalent organic group, and specific examples thereof include those exemplified as a substituent which the nitrogen-containing hetero ring may have in the description of Am ¹ . Further, in the case where a plurality of R ¹ are present in the formula, the plurality of R ^{1 's} may be the same or different from each other.

關於式(A)及式(A-1)中的2個胺基苯基，苯環上的一級胺基的鍵結位置並無特別限定，優選相對於其他基(X¹ 或X² )而言為3位或4位。With respect to the two aminophenyl groups in the formula (A) and the formula (A-1), the bonding position of the primary amine group on the benzene ring is not particularly limited, but is preferably relative to the other group (X ¹ or X ² ). The words are 3 or 4 digits.

作為上述式(A)所表示的化合物(a)的具體例，例如可列舉下述式(A-1-1)~式(A-1-6)所分別表示的化合物。另外，於合成聚醯胺酸時，可單獨使用化合物(a)中的1種或者將2種以上組合使用。Specific examples of the compound (a) represented by the above formula (A) include compounds represented by the following formulas (A-1-1) to (A-1-6). In addition, one type of the compound (a) may be used alone or two or more types may be used in combination in the synthesis of the polyamic acid.

[化5] [Chemical 5]

另外，上述式(A)所表示的化合物(a)具有上述特定結構，並且可獲得耐光性及耐高溫高濕性優異的聚醯胺酸，於此方面考慮，均為具有相同作用的化合物。因此，即使是未於以下實例中記載的化合物亦可於本發明中使用。In addition, the compound (a) represented by the above formula (A) has the above specific structure, and can obtain a polylysine excellent in light resistance and high temperature and high humidity resistance, and in this respect, all compounds having the same action are considered. Therefore, even a compound not described in the following examples can be used in the present invention.

《其他二胺》Other Diamines

用以合成上述聚醯胺酸的二胺可僅使用上述化合物(a)，亦可與上述化合物(a)一同併用其他二胺。The diamine for synthesizing the above polyamic acid may be the same as the above compound (a), or may be used together with the above compound (a) in combination with other diamines.

此處所可使用的其他二胺例如可列舉脂肪族二胺、脂環族二胺、芳香族二胺、二胺基有機矽氧烷等。作為該些的具體例，脂肪族二胺例如可列舉1,3-間苯二甲胺(1,1-metaxylylene diamine)、1,3-丙二胺、四亞甲基二胺、五亞甲基二胺、六亞甲基二胺等； 脂環族二胺例如可列舉1,4-二胺基環己烷、4,4'-亞甲基雙(環己胺)、1,3-雙(胺基甲基)環己烷等； 芳香族二胺例如可列舉鄰苯二胺、間苯二胺、對苯二胺、4,4'-二胺基二苯基甲烷、4,4'-二胺基二苯硫醚、1,5- 二胺基萘、2,2'-二甲基-4,4'-二胺基聯苯、2,2'-雙(三氟甲基)-4,4'-二胺基聯苯、2,7-二胺基茀、4,4'-二胺基二苯醚、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、9,9-雙(4-胺基苯基)茀、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、4,4'-(對伸苯基二異亞丙基)雙苯胺、4,4'-(間伸苯基二異亞丙基)雙苯胺、1,4-雙(4-胺基苯氧基)苯、4,4'-雙(4-胺基苯氧基)聯苯、2,6-二胺基吡啶、3,4-二胺基吡啶、2,4-二胺基嘧啶、3,6-二胺基吖啶、3,6-二胺基哢唑、N-甲基-3,6-二胺基哢唑、N-乙基-3,6-二胺基哢唑、N-苯基-3,6-二胺基哢唑、N,N'-雙(4-胺基苯基)-聯苯胺、N,N'-雙(4-胺基苯基)-N,N'-二甲基聯苯胺、1,4-雙-(4-胺基苯基)-呱嗪、3,5-二胺基苯羧酸、十二烷氧基-2,4-二胺基苯、十四烷氧基-2,4-二胺基苯、十五烷氧基-2,4-二胺基苯、十六烷氧基-2,4-二胺基苯、十八烷氧基-2,4-二胺基苯、十二烷氧基-2,5-二胺基苯、十四烷氧基-2,5-二胺基苯、十五烷氧基-2,5-二胺基苯、十六烷氧基-2,5-二胺基苯、十八烷氧基-2,5-二胺基苯、膽甾烷基氧基-3,5-二胺基苯、膽甾烯基氧基-3,5-二胺基苯、膽甾烷基氧基-2,4-二胺基苯、膽甾烯基氧基-2,4-二胺基苯、3,5-二胺基苯甲酸膽甾烷基酯、3,5-二胺基苯甲酸膽甾烯基酯、3,5-二胺基苯甲酸羊毛甾烷基酯、3,6-雙(4-胺基苯甲醯氧基)膽甾烷、3,6-雙(4-胺基苯氧基)膽甾烷、4-(4'-三氟甲氧基苯甲醯氧基)環己基-3,5-二胺基苯甲酸酯、4-(4'-三氟甲基苯甲醯氧基)環己基-3,5-二胺基苯甲酸酯、1,1-雙(4-((胺基苯基)甲基)苯基)-4-丁基環己烷、1,1-雙 (4-((胺基苯基)甲基)苯基)-4-庚基環己烷、1,1-雙(4-((胺基苯氧基)甲基)苯基)-4-庚基環己烷、1,1-雙(4-((胺基苯基)甲基)苯基)-4-(4-庚基環己基)環己烷、2,4-二胺基-N,N-二烯丙基苯胺、4-胺基苯甲胺(4-Aminobenzylamine)、3-胺基苯甲胺、1-(2,4-二胺基苯基)呱嗪-4-羧酸、4-(嗎啉-4-基)苯-1,3-二胺、1,3-雙(N-(4-胺基苯基)哌啶基)丙烷、1-(4-胺基苯基)-2,3-二氫-1,3,3-三甲基-1H-茚-5-胺、1-(4-胺基苯基)-2,3-二氫-1,3,3-三甲基-1H-茚-6-胺、4-胺基苯基-4'-胺基苯甲酸酯、4,4'-[4,4'-丙烷-1,3-二基雙(哌啶-1,4-二基)]二苯胺、及下述式(D-1)所表示的化合物等， Examples of the other diamine which can be used herein include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamine organodecane, and the like. Specific examples of the aliphatic diamine include, for example, 1,1-metaxylylene diamine, 1,3-propanediamine, tetramethylenediamine, and penta. Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4′-methylenebis(cyclohexylamine), and 1,3-. Bis(aminomethyl)cyclohexane or the like; examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4, 4 '-Diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl) )-4,4'-diaminobiphenyl, 2,7-diamino fluorene, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-double (4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediisopropylidene)diphenylamine, 4,4'-(meta-phenyldiisopropylidene)diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diamine Pyridine, 2,4-diaminopyrimidine, 3,6-diamino Pyridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6 -diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine , 1,4-bis-(4-aminophenyl)-pyridazine, 3,5-diaminobenzenecarboxylic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy -2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4- Diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, Hexadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholesteryl Oxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestyloxy-2,4-diaminobenzene, 3,5-diamine Cholesteryl benzoate, cholesteryl 3,5-diaminobenzoate, lanostino 3,5-diaminobenzoic acid, 3,6-bis(4-aminobenzene Methoxyoxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzene Methoxyoxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzyloxy)cyclohexyl-3,5-diaminobenzoate 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)benzene) 4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4- ((Aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2,4-diamino-N,N-diallylaniline, 4-amino 4-Aminobenzylamine, 3-aminobenzylamine, 1-(2,4-diaminophenyl)pyridazine-4-carboxylic acid, 4-(morpholin-4-yl)benzene- 1,3-Diamine, 1,3-bis(N-(4-aminophenyl)piperidinyl)propane, 1-(4-aminophenyl)-2,3-dihydro-1,3 ,3-trimethyl-1H-indole-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-6-amine 4-aminophenyl-4'-aminobenzoic acid ester, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)] Diphenylamine, a compound represented by the following formula (D-1), etc.

式(D-1)中，X^I 及X^II 分別為單鍵、-O-、-COO-或-OCO-，R^I 是碳數為1~3的烷二基，a為0或1，b為0~2的整數，c為1~20的整數，n為0或1。其中，a及b並不同時為0； 二胺基有機矽氧烷例如分別可列舉1,3-雙(3-胺基丙基)-四甲基二矽氧烷等；除此以外亦可使用日本專利特開2010-97188號公報中所記載的二胺。In the formula (D-1), X ^I and X ^II are each a single bond, -O-, -COO- or -OCO-, and R ^I is an alkanediyl group having a carbon number of 1 to 3, and a is 0 or 1, b is an integer from 0 to 2, c is an integer from 1 to 20, and n is 0 or 1. Wherein, a and b are not 0 at the same time; for example, 1,3-bis(3-aminopropyl)-tetramethyldioxane and the like are respectively exemplified as the diaminoorganomethoxy oxane; The diamine described in JP-A-2010-97188 is used.

上述式(D-1)中的“-X^I -(R^I -X^II )_n -”所表示的2價基優選為碳數為1~3的烷二基、*-O-、*-COO-或*-O-C₂ H₄ -O-(其中，附有“*”的鍵與二胺基苯基鍵結)。The divalent group represented by "-X ^I -(R ^I -X ^II ) _n -" in the above formula (D-1) is preferably an alkanediyl group having a carbon number of 1 to 3, *-O-, *- COO- or *-OC ₂ H ₄ -O- (wherein a bond with a "*" is bonded to a diaminophenyl group).

作為基“-C_c H_2c+1 ”的具體例，例如可列舉甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、正十九烷基、正二十烷基等。二胺基苯基中的2個胺基相對於其他基而言優選為2,4-位或3,5-位。Specific examples of the group "-C _c H _2c+1 " include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-decyl group. , n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nine Alkyl, n-icosyl, and the like. The two amine groups in the diaminophenyl group are preferably the 2,4-position or the 3,5-position relative to the other groups.

作為上述式(D-1)所表示的化合物的具體例，例如可列舉下述式(D-1-1)~式(D-1-3)所分別表示的化合物等。Specific examples of the compound represented by the above formula (D-1) include a compound represented by the following formula (D-1-1) to formula (D-1-3), and the like.

另外，在上述聚醯胺酸的合成中所使用的其他二胺可單獨使用1種上述化合物或者將2種以上組合使用。In addition, one type of the above-mentioned compounds may be used alone or two or more types may be used in combination in the other diamine used for the synthesis of the above polyamic acid.

作為本發明中的聚醯胺酸的合成中所使用的二胺，於可確保液晶顯示元件的耐光性及耐高溫高濕性或液晶配向膜的再加工性的方面而言，化合物(a)的比率優選為相對於合成中所使用的二胺的總量而言為0.1 mol%以上。自可使初始電壓保持率更良好的方面考慮，該比率更優選為0.1 mol%~70 mol%。進一步更優選為5 mol%~50 mol%，特別優選為10 mol%~50 mol%。The diamine used in the synthesis of the polyamic acid in the present invention is a compound (a) in terms of ensuring light resistance, high temperature and high humidity resistance of the liquid crystal display element, or reworkability of the liquid crystal alignment film. The ratio is preferably 0.1 mol% or more based on the total amount of the diamine used in the synthesis. The ratio is more preferably 0.1 in terms of making the initial voltage holding ratio better. Mol%~70 mol%. It is more preferably 5 mol% to 50 mol%, particularly preferably 10 mol% to 50 mol%.

[分子量調節劑][Molecular weight regulator]

於合成聚醯胺酸時，亦可與如上所述的四羧酸二酐及二胺一同使用適當的分子量調節劑而合成末端改質型聚合物。通過製成該末端改質型的聚合物，可不損及本發明的效果地進一步改善液晶配向劑的塗布性(印刷性)。In the case of synthesizing polyamic acid, a terminal-modified polymer may be synthesized by using an appropriate molecular weight modifier together with the tetracarboxylic dianhydride and the diamine as described above. By forming the terminal-modified polymer, the coating property (printability) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention.

分子量調節劑例如可列舉酸單酐、單胺化合物、單異氰酸酯化合物等。作為該些化合物的具體例，酸單酐例如可列舉馬來酸酐、鄰苯二甲酸酐、衣康酸酐、正癸基琥珀酸酐、正十二烷基琥珀酸酐、正十四烷基琥珀酸酐、正十六烷基琥珀酸酐等；單胺化合物例如可列舉苯胺、環己胺、正丁胺、正戊胺、正己胺、正庚胺、正辛胺等；單異氰酸酯化合物例如可列舉異氰酸苯酯、異氰酸萘酯等。Examples of the molecular weight modifier include an acid monoanhydride, a monoamine compound, and a monoisocyanate compound. Specific examples of the compounds include, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, and the like. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, and the like; and the monoisocyanate compound may, for example, beocyanic acid. Phenyl ester, naphthyl isocyanate, and the like.

相對於所使用的四羧酸二酐及二胺的合計100重量份而言，分子量調節劑的使用比例優選為20重量份以下，更優選為10重量份以下。The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine to be used.

<化合物(a)的合成><Synthesis of Compound (a)>

本發明的化合物(a)可通過將有機化學的常規方法適宜組合而合成。作為其一例，例如可列舉合成以2個硝基苯基代替上述式(A)中的2個胺基苯基的二硝基體，其後使用適當的還原系對所得的二硝基體的硝基進行氫化 而胺化的方法。The compound (a) of the present invention can be synthesized by a suitable combination of a conventional method of organic chemistry. As an example, for example, a dinitro group in which two aminophenyl groups in the above formula (A) are replaced by two nitrophenyl groups is synthesized, and then the nitro group of the obtained dinitro group is used using an appropriate reduction system. Hydrogenation And the method of amination.

此處，上述二硝基體在X¹ 為“*-COO-”或“*-COO-Ar¹ -”的情況下，例如可通過如下方式而合成：使硝基氟苯等含有硝基苯基的鹵化物與具有羧基的二級環式胺化合物反應，使由此而所得的反應生成物與具有硝基苯基的羥基衍生物反應。Here, when the X ¹ is "*-COO-" or "*-COO-Ar ¹ -", the dinitro group can be synthesized, for example, by including a nitrophenyl group such as nitrofluorobenzene or the like. The halide is reacted with a secondary cyclic amine compound having a carboxyl group, and the reaction product thus obtained is reacted with a hydroxy derivative having a nitrophenyl group.

而且，在X¹ 為“*-OCO-”或“*-R³ -OCO-”的情況下，例如可通過如下方式而合成：使硝基氟苯等含有硝基苯基的鹵化物與具有羥基的環式二級胺化合物反應，使由此而所得的反應生成物與硝基苯甲醯氯等含有硝基苯基的羧醯鹵化合物反應。Further, in the case where X ¹ is "*-OCO-" or "*-R ³ -OCO-", it can be synthesized, for example, by using a nitrophenyl group-containing halide such as nitrofluorobenzene or the like. The cyclic secondary amine compound of a hydroxyl group is reacted, and the reaction product thus obtained is reacted with a carboxyphenyl halide compound containing a nitrophenyl group such as nitrobenzimid chloride.

在X¹ 為“-NH-”的情況下，例如可通過使硝基氟苯等含有硝基苯基的鹵化物與具有一級胺基的環式二級胺化合物反應而獲得上述二硝基體。In the case where X ¹ is "-NH-", the above dinitro group can be obtained, for example, by reacting a nitrophenyl group-containing halide such as nitrofluorobenzene with a cyclic secondary amine compound having a primary amine group.

而且，在X¹ 為“*-Ar¹ -O-”的情況下，例如可通過使含有硝基苯基的鹵化物與具有基“-Ar¹ -OH”的環式二級胺化合物反應而合成上述二硝基體；在X¹ 為“*-O-Ar¹ -”的情況下，可通過使羥基哌啶等含有羥基的環式二級胺化合物與對應的含有硝基苯基的鹵化物反應而獲得上述二硝基體。Further, in the case where X ¹ is "*-Ar ¹ -O-", for example, by reacting a halide containing a nitrophenyl group with a cyclic secondary amine compound having a group "-Ar ¹ -OH" The above dinitrogen is synthesized; in the case where X ¹ is "*-O-Ar ¹ -", a cyclic secondary amine compound having a hydroxyl group such as hydroxypiperidine and a corresponding nitrophenyl group-containing halide can be obtained. The above dinitrogen is obtained by the reaction.

用以獲得上述作為中間體的二硝基體的反應優選在有機溶劑中進行。此時的反應溫度優選為-20℃~180℃，更優選為0℃~120℃。而且，反應時間優選為0.1小時~24小時，更優選為0.5小時~12小時。The reaction for obtaining the above dinitrogen as an intermediate is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 180 ° C, and more preferably 0 ° C to 120 ° C. Further, the reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

有機溶劑可使用在取代反應時所通常使用的化合 物，具體而言例如可列舉甲醇、乙醇、四氫呋喃、甲苯、二甲基亞碸、二甲基甲醯胺、二甲基乙醯胺、1-甲基-2-吡咯烷酮等。而且，於反應時，亦可視需要而加入碳酸氫鈉、碳酸鉀、碳酸鋰、三乙胺等鹼；二甲基胺基吡啶等親核劑；1-(3-二甲基胺基丙基)-3-乙基碳二醯亞胺鹽酸鹽(EDC)等脫水縮合劑等添加劑。The organic solvent can be used in the compound which is usually used in the substitution reaction. Specific examples thereof include methanol, ethanol, tetrahydrofuran, toluene, dimethyl hydrazine, dimethylformamide, dimethylacetamide, and 1-methyl-2-pyrrolidone. Further, in the reaction, a base such as sodium hydrogencarbonate, potassium carbonate, lithium carbonate or triethylamine may be added as needed; a nucleophilic agent such as dimethylaminopyridine; 1-(3-dimethylaminopropyl group); An additive such as a dehydrating condensing agent such as 3-ethylcarbodiimide hydrochloride (EDC).

上述中間體的還原反應例如可使用鋅、氫化鋁鋰、鈀催化劑-氫系等而實施。此時的反應溫度優選為-20℃~180℃，更優選為10℃~120℃。而且，反應時間優選為0.1小時~72小時，更優選為0.5小時~48小時。然而，化合物(a)的合成順序並不限定於上述方法。The reduction reaction of the above intermediate can be carried out, for example, by using zinc, lithium aluminum hydride, a palladium catalyst-hydrogen type or the like. The reaction temperature at this time is preferably -20 ° C to 180 ° C, and more preferably 10 ° C to 120 ° C. Further, the reaction time is preferably from 0.1 to 72 hours, more preferably from 0.5 to 48 hours. However, the order of synthesis of the compound (a) is not limited to the above method.

<聚醯胺酸的合成><Synthesis of polylysine>

作為提供至本發明的聚醯胺酸的合成反應的四羧酸二酐與二胺的使用比例，優選相對於二胺的胺基1當量而言，四羧酸二酐的酸酐基成為0.2當量~2當量的比例，更優選成為0.3當量~1.2當量的比例。The ratio of use of the tetracarboxylic dianhydride to the diamine to be used in the synthesis reaction of the polyaminic acid of the present invention is preferably such that the acid anhydride group of the tetracarboxylic dianhydride becomes 0.2 equivalent based on 1 equivalent of the amine group of the diamine. The ratio of ~2 equivalents is more preferably a ratio of 0.3 equivalents to 1.2 equivalents.

聚醯胺酸的合成反應優選於有機溶劑中進行。此時的反應溫度優選為-20℃~150℃，更優選為0℃~100℃。而且，反應時間優選為0.1小時~24小時，更優選為0.5小時~12小時。The synthesis reaction of polylysine is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. Further, the reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

此處，有機溶劑例如可列舉非質子性極性溶劑、酚及其衍生物、醇、酮、酯、醚、鹵代烴、烴等。Here, examples of the organic solvent include an aprotic polar solvent, a phenol and a derivative thereof, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, and the like.

作為該些有機溶劑的具體例，上述非質子性極性溶劑例如可列舉N-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N- 二甲基甲醯胺、二甲基亞碸、γ-丁內酯、四甲基脲、六甲基磷醯三胺等；上述酚衍生物例如可列舉間甲酚、二甲苯酚、鹵代酚等；上述醇例如可列舉甲醇、乙醇、異丙醇、環己醇、乙二醇、丙二醇、1,4-丁二醇、三乙二醇、乙二醇單甲醚等；上述酮例如可列舉丙酮、甲基乙基酮、甲基異丁基酮、環己酮等；上述酯例如可列舉乳酸乙酯、乳酸丁酯、乙酸甲酯、乙酸乙酯、乙酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、草酸二乙酯、丙二酸二乙酯等；上述醚例如可列舉二***、乙二醇甲醚、乙二醇***、乙二醇正丙醚、乙二醇異丙醚、乙二醇正丁醚、乙二醇二甲醚、乙二醇***乙酸酯、二乙二醇二甲醚、二乙二醇二***、二乙二醇單甲醚、二乙二醇單***、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、四氫呋喃等；上述鹵代烴例如可列舉二氯甲烷、1,2-二氯乙烷、1,4-二氯丁烷、三氯乙烷、氯苯、鄰二氯苯等；上述烴例如可列舉己烷、庚烷、辛烷、苯、甲苯、二甲苯、丙酸異戊酯、異丁酸異戊酯、二異戊醚等。Specific examples of the organic solvent include, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-. Dimethylformamide, dimethyl hydrazine, γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine, etc.; the above phenol derivatives include, for example, m-cresol, xylenol, halogenated Phenol or the like; examples of the above alcohol include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, and the like; Examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, and methoxy group. Methyl propionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, etc.; examples of the above ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol diethyl ether, and ethylene glycol n-propyl ether. , ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc.; the above halogenated hydrocarbon may, for example, be dichloromethane. 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, etc.; examples of the above hydrocarbons include hexane, heptane, octane, benzene, toluene, Xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like.

於該些有機溶劑中，優選使用選自由非質子性極性溶劑以及酚及其衍生物所構成的群組(第一群組的有機溶劑)的一種以上、或者選自第一群組的有機溶劑的一種以上與選自由醇、酮、酯、醚、鹵代烴及烴所構成的群組(第二 群組的有機溶劑)的一種以上的混合物。在後者的情況下，作為第二群組的有機溶劑的使用比例，相對於第一群組的有機溶劑及第二群組的有機溶劑的合計量而言優選為50重量%以下，更優選為40重量%以下，進一步更優選為30重量%以下。Among the organic solvents, it is preferred to use one or more selected from the group consisting of an aprotic polar solvent and a phenol and a derivative thereof (the first group of organic solvents), or an organic solvent selected from the first group. One or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (second More than one mixture of groups of organic solvents). In the latter case, the ratio of use of the organic solvent as the second group is preferably 50% by weight or less based on the total amount of the organic solvent of the first group and the organic solvent of the second group, and more preferably 40% by weight or less, and still more preferably 30% by weight or less.

有機溶劑的使用量(a)優選設為如下的量：四羧酸二酐及二胺的合計量(b)相對於反應溶液的總量(a+b)而言成為0.1重量%~50重量%的量。The amount (a) of the organic solvent to be used is preferably such an amount that the total amount of the tetracarboxylic dianhydride and the diamine (b) is from 0.1% by weight to 50% by weight based on the total amount of the reaction solution (a+b). The amount of %.

如上所述而獲得使聚醯胺酸溶解而成的反應溶液。該反應溶液可直接供至液晶配向劑的調製，也可以使反應溶液中所含的聚醯胺酸離析後供至液晶配向劑的調製，或者對離析的聚醯胺酸進行純化後供至液晶配向劑的調製。於使聚醯胺酸進行脫水閉環而製成聚醯亞胺的情況時，可將上述反應溶液直接供至脫水閉環反應，亦可將反應溶液中所含的聚醯胺酸離析後供至脫水閉環反應，或者對離析的聚醯胺酸進行純化後供至脫水閉環反應。聚醯胺酸的離析及純化可依照公知的方法而進行。A reaction solution obtained by dissolving polylysine was obtained as described above. The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be prepared by isolating the polylysine contained in the reaction solution to the liquid crystal alignment agent, or purifying the isolated polyamic acid to the liquid crystal. Modulation of the alignment agent. When polylysine is subjected to dehydration ring closure to form a polyimine, the reaction solution may be directly supplied to a dehydration ring-closure reaction, or the polylysine contained in the reaction solution may be isolated and dehydrated. The ring closure reaction, or the isolated polylysine is purified and supplied to the dehydration ring closure reaction. The isolation and purification of polylysine can be carried out in accordance with a known method.

<聚醯亞胺及聚醯亞胺的合成><Synthesis of Polyimine and Polyimine>

本發明的液晶配向劑中所含的聚醯亞胺可通過對如上所述而合成的聚醯胺酸進行脫水閉環將其醯亞胺化而獲得。The polyimine contained in the liquid crystal alignment agent of the present invention can be obtained by subjecting the polylysine synthesized as described above to dehydration ring closure to imidize the ruthenium.

上述聚醯亞胺可以是作為其前驅體的聚醯胺酸所具有的醯胺酸結構全部脫水閉環而成的完全醯亞胺化物，亦可為醯胺酸結構的僅僅一部分脫水閉環、醯胺酸結構與醯 亞胺環結構並存的部分醯亞胺化物。作為本發明中的聚醯亞胺，其醯亞胺化率優選為30%以上，更優選為40%~99%，進一步更優選為50%~99%。該醯亞胺化率是以百分率表示醯亞胺環結構數相對於聚醯亞胺的醯胺酸結構數與醯亞胺環結構數的合計所占的比例。此處，醯亞胺環的一部分亦可為異醯亞胺環。The polyimine may be a fully ruthenium imide formed by dehydration ring closure of a proline structure of polyglycine as a precursor thereof, or may be only a part of a guanamine structure, dehydration ring closure, guanamine Acid structure and enthalpy Part of the quinone imine compound coexisting with the imine ring structure. The polyamidene in the present invention preferably has a ruthenium iodide ratio of 30% or more, more preferably 40% to 99%, still more preferably 50% to 99%. The ruthenium imidization ratio is a ratio of the number of quinone ring structures to the total number of guanidine structures and the number of quinone ring structures of the polyimine. Here, a part of the quinone ring may also be an isoindole ring.

聚醯胺酸的脫水閉環優選通過如下方法而進行：對聚醯胺酸進行加熱的方法；或者將聚醯胺酸溶解於有機溶劑中，於該溶液中添加脫水劑及脫水閉環催化劑而視需要進行加熱的方法。其中優選利用後者的方法。The dehydration ring closure of polylysine is preferably carried out by a method of heating polylysine; or dissolving polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, as needed The method of heating. Among them, the latter method is preferably used.

於上述聚醯胺酸溶液中添加脫水劑及脫水閉環催化劑的方法中，脫水劑例如可使用乙酸酐、丙酸酐、三氟乙酸酐等酸酐。作為脫水劑的使用量，相對於聚醯胺酸的醯胺酸結構1莫耳而言優選為0.01莫耳~20莫耳。脫水閉環催化劑例如可使用吡啶、三甲吡啶、二甲吡啶、三乙胺等三級胺。作為脫水閉環催化劑的使用量，相對於所使用的脫水劑1莫耳而言優選為0.01莫耳~10莫耳。作為脫水閉環反應中所使用的有機溶劑，可列舉作為聚醯胺酸的合成中所使用的有機溶劑而例示的有機溶劑。脫水閉環反應的反應溫度優選為0℃~180℃，更優選為10℃~150℃。反應時間優選為1.0小時~120小時，更優選為2.0小時~30小時。In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the above polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 mol to 20 mol with respect to the proline structure of polylysine. As the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. The amount of use as the dehydration ring-closure catalyst is preferably 0.01 mol to 10 mol per mol of the dehydrating agent used. The organic solvent used for the dehydration ring-closure reaction is exemplified as an organic solvent exemplified as the organic solvent used in the synthesis of polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 ° C to 180 ° C, more preferably from 10 ° C to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

如此進行而獲得含有聚醯亞胺的反應溶液。該反應溶液可直接供至液晶配向劑的調製，也可以自反應溶液中除 去脫水劑及脫水閉環催化劑後而供至液晶配向劑的調製，也可以使聚醯亞胺離析後而供至液晶配向劑的調製，或者也可以對離析的聚醯亞胺進行純化後供至液晶配向劑的調製。該些純化操作可依照公知的方法而進行。This was carried out to obtain a reaction solution containing polyimine. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or can be removed from the reaction solution. After dehydrating agent and dehydration ring-closing catalyst are supplied to the liquid crystal alignment agent, the polyimine may be isolated and supplied to the liquid crystal alignment agent, or the isolated polyimine may be purified and then supplied. Modulation of liquid crystal alignment agent. These purification operations can be carried out in accordance with a known method.

<聚合物的溶液黏度、分子量><Solid viscosity and molecular weight of polymer>

作為如上所述而所得的聚醯胺酸及聚醯亞胺，於將其製成濃度為10重量%的溶液時，優選具有10 mPa．s~800 mPa．s的溶液黏度，更優選具有15 mPa．s~500 mPa．s的溶液黏度。另外，上述聚合物的溶液黏度(mPa．s)是對使用該聚合物的良溶劑(例如γ-丁內酯、N-甲基-2-吡咯烷酮等)而調製的濃度為10重量%的聚合物溶液，使用E型旋轉黏度計而於25℃下所測定的值。The poly-proline and polyimine obtained as described above, when it is made into a solution having a concentration of 10% by weight, preferably has 10 mPa. s~800 mPa. The solution viscosity of s is more preferably 15 mPa. s~500 mPa. s solution viscosity. Further, the solution viscosity (mPa.s) of the above polymer is a polymerization having a concentration of 10% by weight prepared by using a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer. The solution was measured at 25 ° C using an E-type rotational viscometer.

上述聚醯胺酸、聚醯亞胺的利用凝膠滲透色譜法(Gel Permeation Chromatography，GPC)而測定的聚苯乙烯換算的重量平均分子量(Mw)優選為1,000~500,000，更優選為2，000~300,000。而且，以Mw與利用GPC而測定的聚苯乙烯換算的數量平均分子量(Mn)的比所表示的分子量分佈(Mw/Mn)優選為15以下，更優選為10以下。通過使其為此種分子量範圍，可確保液晶顯示元件的良好的配向性及穩定性。The polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the poly-proline and polyimine is preferably 1,000 to 500,000, more preferably 2,000. ~300,000. In addition, the molecular weight distribution (Mw/Mn) expressed by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, and more preferably 10 or less. By making it such a molecular weight range, good alignment and stability of a liquid crystal display element can be ensured.

<其他添加劑><Other additives>

本發明的液晶配向劑含有如上所述的聚醯胺酸及聚醯亞胺的至少任意種聚合物(以下亦稱為“特定聚合物”)，亦可視需要含有其他成分。該其他成分例如可列舉上述特 定聚合物以外的其他聚合物、於分子內具有至少一個環氧基的化合物(以下稱為“含有環氧基的化合物”)、抗氧化劑、多官能(甲基)丙烯酸酯、官能性矽烷化合物等。The liquid crystal alignment agent of the present invention contains at least any polymer (hereinafter also referred to as "specific polymer") of polyamic acid and polyimine as described above, and may contain other components as needed. Examples of the other components include the above-mentioned special components. a polymer other than a polymer, a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compound"), an antioxidant, a polyfunctional (meth) acrylate, a functional decane compound Wait.

[其他聚合物][Other polymers]

上述其他聚合物可用以改善溶液特性或電氣特性。該其他聚合物例如可列舉使上述例示的四羧酸二酐與不含化合物(a)的二胺化合物反應而所得的聚醯胺酸(以下稱為“其他聚醯胺酸”)、該其他聚醯胺酸進行脫水閉環而成的聚醯亞胺(以下稱為“其他聚醯亞胺”)、聚醯胺酸酯、聚酯、聚醯胺、聚矽氧烷、纖維素衍生物、聚甲醛、聚苯乙烯衍生物、聚(苯乙烯-苯基馬來醯亞胺)衍生物、聚(甲基)丙烯酸酯等。The other polymers described above can be used to improve solution properties or electrical properties. The other polymer may, for example, be a poly-proline (hereinafter referred to as "other poly-proline") obtained by reacting the above-exemplified tetracarboxylic dianhydride with a diamine compound containing no compound (a), and the like. Polyimine which is obtained by dehydration ring closure of polylysine (hereinafter referred to as "other polyimine"), polyphthalate, polyester, polyamine, polyoxane, cellulose derivative, Polyoxymethylene, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like.

於將其他聚合物添加於液晶配向劑中時，相對於該組成物中的所有聚合物量而言，其調配比率優選為50重量%以下，更優選為0.1重量%~40重量%，進一步更優選為0.1重量%~30重量%。When the other polymer is added to the liquid crystal alignment agent, the compounding ratio is preferably 50% by weight or less, more preferably 0.1% by weight to 40% by weight, even more preferably based on the total amount of the polymer in the composition. It is from 0.1% by weight to 30% by weight.

[含有環氧基的化合物][Epoxy group-containing compound]

含有環氧基的化合物可用以使液晶配向膜的與基板表面的接著性提高。此處，含有環氧基的化合物例如可列舉乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、甘油二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、2,2-二溴新戊二醇二縮水甘油醚、N,N,N',N'-四縮水甘油基-間 苯二甲胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷、N,N-二縮水甘油基-苯甲胺、N,N-二縮水甘油基-胺基甲基環己烷、N,N-二縮水甘油基-環己胺、國際公開第2009/096598號中所記載的含有環氧基的聚有機矽氧烷等作為優選的含有環氧基的化合物。The epoxy group-containing compound can be used to improve the adhesion of the liquid crystal alignment film to the surface of the substrate. Here, examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and new Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether , N, N, N', N'-tetraglycidyl - between Xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diamine Diphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, international The epoxy group-containing polyorganosiloxane or the like described in JP/A No. 2009/096598 is preferably a compound containing an epoxy group.

於將該些含有環氧基的化合物添加於液晶配向劑中時，相對於液晶配向劑中所含的聚合物的合計100重量份而言，其調配比率優選為40重量份以下，更優選為0.1重量份~30重量份。When the epoxy group-containing compound is added to the liquid crystal alignment agent, the compounding ratio is preferably 40 parts by weight or less based on 100 parts by weight of the total of the polymer contained in the liquid crystal alignment agent, and more preferably 0.1 parts by weight to 30 parts by weight.

[抗氧化劑][Antioxidants]

以如下的目的而使用抗氧化劑：使紫外線或熱等能量作為誘因而產生的過氧自由基或氫過氧化物無效化，抑制液晶顯示元件的電氣特性降低。抗氧化劑例如可列舉酚類抗氧化劑、胺類抗氧化劑、磷類抗氧化劑、硫類抗氧化劑及該些的摻合化合物等。該些抗氧化劑例如可使用市售品，作為其具體例，酚類抗氧化劑例如可列舉Adekastab AO-20、Adekastab AO-30、Adekastab AO-40、Adekastab AO-50、Adekastab AO-60(以上為艾迪科(ADEKA)公司製造)、IRGANOX1010、IRGANOX1035、IRGAOX1076等IRGANOX系列、IRGAMOD295等IRGAMOD系列(以上由巴斯夫日本(BASF Japan)製造)等；胺類抗氧化劑例如可列舉Adekastab LA-52、LA-63等Adekastab LA系列(ADEKA公司製造)、CHIMASSORB119等 CHIMASSORB系列、TINUVIN622、TINUVIN123等TINUVIN系列(以上由BASF Japan製造)等；An antioxidant is used for the purpose of invalidating peroxy radicals or hydroperoxides which are generated by the use of energy such as ultraviolet rays or heat, thereby suppressing deterioration of electrical characteristics of the liquid crystal display element. Examples of the antioxidant include a phenol antioxidant, an amine antioxidant, a phosphorus antioxidant, a sulfur antioxidant, and a blending compound thereof. As the antioxidant, for example, a commercially available product can be used, and specific examples thereof include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, and Adekastab AO-60 (the above is IRGANOX series such as IRGANOX1010, IRGANOX1035, and IRGAOX1076, IRGAMOD series such as IRGAMOD295 (above, manufactured by BASF Japan), etc.; and amine-based antioxidants include, for example, Adekastab LA-52, LA- 63 Adekastab LA series (made by ADEKA), CHIMASSORB119, etc. TINMASVIN series, TINUVIN 622, TINUVIN123, etc. (the above is manufactured by BASF Japan);

磷類抗氧化劑例如可列舉Adekastab PEP-4C、Adekastab PEP-8、HP-10、2112(以上由ADEKA公司製造)、IRGAFOS168、GSY-P101(以上由堺化學工業公司製造)、IRGAFOS168等IRGAFOS系列、IRGAFOS P-EPQ(以上由BASF Japan製造)等；硫類抗氧化劑例如可列舉Adekastab AO-412、Adekastab AO-503(以上由ADEKA公司製造)、IRGANOX PS 800、IRGANOX PS 802(以上由BASF Japan製造)等；摻合類抗氧化劑例如可列舉Adekastab A-611、Adekastab A-612、Adekastab AO-37、Adekastab AO-15(以上由ADEKA公司製造)、TINUVIN111等TINUVIN系列(以上由BASF Japan製造)等。另外，抗氧化劑可使用上述中的1種或者將2種以上組合使用。Examples of the phosphorus-based antioxidant include Adekastab PEP-4C, Adekastab PEP-8, HP-10, 2112 (manufactured by ADEKA CORPORATION), IRGAFOS168, GSY-P101 (manufactured by Daicel Chemical Industries, Ltd.), IRGAFOS168, and other IRGAFOS series. IRGAFOS P-EPQ (manufactured by BASF Japan) or the like; examples of the sulfur-based antioxidant include Adekastab AO-412, Adekastab AO-503 (above manufactured by ADEKA), IRGANOX PS 800, and IRGANOX PS 802 (above manufactured by BASF Japan) And the like, for example, Adekastab A-611, Adekastab A-612, Adekastab AO-37, Adekastab AO-15 (above, manufactured by ADEKA), TINUVIN series such as TINUVIN 111 (above, manufactured by BASF Japan), etc. . Further, one type of the above-mentioned antioxidants may be used or two or more types may be used in combination.

作為所使用的抗氧化劑，其中優選酚類抗氧化劑、胺類抗氧化劑。而且，於將該些抗氧化劑添加於液晶配向劑中的情況下，相對於聚合物的合計100重量份而言，其調配比率優選為10重量份以下，更優選為5重量份以下，進一步更優選為0.1重量份~3重量份。Among the antioxidants to be used, preferred are phenolic antioxidants and amine antioxidants. In addition, when the antioxidant is added to the liquid crystal alignment agent, the compounding ratio is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and further more, based on 100 parts by weight of the total of the polymer. It is preferably 0.1 parts by weight to 3 parts by weight.

[多官能(甲基)丙烯酸酯][Polyfunctional (meth) acrylate]

多官能(甲基)丙烯酸酯可用以使液晶顯示元件的耐候性提高。多官能(甲基)丙烯酸酯例如可列舉乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、1,6-己二醇二丙烯酸酯、 1,6-己二醇二甲基丙烯酸脂、1,9-壬二醇二丙烯酸酯、1,9-壬二醇二甲基丙烯酸脂、四乙二醇二丙烯酸酯、四乙二醇二甲基丙烯酸酯、聚丙二醇二丙烯酸酯、聚丙二醇二甲基丙烯酸脂、雙苯氧基乙醇茀二丙烯酸酯、雙苯氧基乙醇茀二甲基丙烯酸脂、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇六甲基丙烯酸酯、磷酸三(2-丙烯醯氧基乙基)酯、磷酸三(2-甲基丙烯醯氧基乙基)酯等。另外，多官能(甲基)丙烯酸酯亦可使用市售品。A polyfunctional (meth) acrylate can be used to improve the weather resistance of the liquid crystal display element. Examples of the polyfunctional (meth) acrylate include ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,6-hexanediol diacrylate. 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol Methacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, bisphenoxyethanol hydrazine diacrylate, bisphenoxyethanol hydrazine dimethacrylate, trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, Pentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tris(2-propenyloxyethyl) phosphate, tris(2-methylpropenyloxyethyl) phosphate, and the like. Further, a commercially available product can also be used as the polyfunctional (meth) acrylate.

於將該些多官能(甲基)丙烯酸酯添加於液晶配向劑中的情況下，相對於聚合物的合計100重量份而言，其調配比率優選為100重量份以下，更優選為50重量份以下，進一步更優選為0.1重量份~30重量份。In the case where the polyfunctional (meth) acrylate is added to the liquid crystal alignment agent, the compounding ratio is preferably 100 parts by weight or less, more preferably 50 parts by weight, based on 100 parts by total of the total of the polymer. Hereinafter, it is more preferably 0.1 part by weight to 30 parts by weight.

[官能性矽烷化合物][functional decane compound]

上述官能性矽烷化合物可用以使液晶配向劑的印刷性提高。此種官能性矽烷化合物例如可列舉3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、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-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、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-三乙氧基矽烷基 丙基三乙撐三胺、N-三甲氧基矽烷基丙基三乙撐三胺、10-三甲氧基矽烷基-1,4,7-三氮雜癸烷、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三甲氧基矽烷基-3,6-二氮雜壬酸甲酯、9-三乙氧基矽烷基-3,6-二氮雜壬酸甲酯、N-苄基-3-胺基丙基三甲氧基矽烷、N-苄基-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、縮水甘油氧基甲基三甲氧基矽烷、縮水甘油氧基甲基三乙氧基矽烷、2-縮水甘油氧基乙基三甲氧基矽烷、2-縮水甘油氧基乙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷等。The above functional decane compound can be used to improve the printability of the liquid crystal alignment agent. Examples of such a functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltri Ethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Decane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl- 3-aminopropyltriethoxydecane, N-triethoxydecane Propyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecane Base-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3,6-diaza Heteroyl acetate, methyl 9-trimethoxydecyl-3,6-diazadecanoate, methyl 9-triethoxydecyl-3,6-diazadecanoate, N- Benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-benzene 3-aminopropyltriethoxydecane, glycidoxymethyltrimethoxydecane, glycidoxymethyltriethoxydecane, 2-glycidoxyethyltrimethoxydecane, 2-glycidoxyethyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and the like.

於將該些官能性矽烷化合物添加於液晶配向劑中的情況下，相對於聚合物的合計100重量份而言，其調配比率優選為2重量份以下，更優選為0.02重量份~0.2重量份。In the case where the functional decane compound is added to the liquid crystal alignment agent, the compounding ratio is preferably 2 parts by weight or less, more preferably 0.02 parts by weight to 0.2 parts by weight based on 100 parts by weight of the total of the polymer. .

<溶劑><solvent>

本發明的液晶配向劑是聚合物成分及視需要而任意地調配的其他添加劑優選溶解於有機溶劑中而構成。The liquid crystal alignment agent of the present invention is preferably a polymer component and optionally other additives which are optionally formulated in an organic solvent.

所使用的有機溶劑例如可列舉N-甲基-2-吡咯烷酮、γ-丁內酯、γ-丁內醯胺、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、4-羥基-4-甲基-2-戊酮、乙二醇單甲醚、乳酸丁酯、乙酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、乙二醇甲醚、乙二醇***、乙二醇正丙醚、乙二醇異丙醚、乙二醇 正丁醚(丁基溶纖劑)、乙二醇二甲醚、乙二醇***乙酸酯、二乙二醇二甲醚、二乙二醇二***、二乙二醇單甲醚、二乙二醇單***、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、二異甲基乙基酮、丙酸異戊酯、異丁酸異戊酯、二異戊醚、碳酸乙二酯、碳酸丙二酯等。該些有機溶劑可單獨使用或者將2種以上混合使用。Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, and N,N-dimethylacetamidine. Amine, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol Methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol N-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene Alcohol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisomethyl ethyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether , ethylene carbonate, propylene carbonate and the like. These organic solvents may be used singly or in combination of two or more.

本發明的液晶配向劑中的固形物濃度(液晶配向劑中的除溶劑以外的成分的合計重量於液晶配向劑的總重量中所占的比例)可考慮黏性、揮發性等而適宜選擇，優選為1重量%~10重量%的範圍。亦即，本發明的液晶配向劑通過如後所述地塗布在基板表面，優選進行加熱，由此而形成作為液晶配向膜的塗膜或者成為液晶配向膜的塗膜。此時，在固形物濃度不足1重量%的情況下，該塗膜的膜厚變得過小而難以獲得良好的液晶配向膜。另一方面，在固形物濃度超過10重量%的情況下，塗膜的膜厚變得過大而難以獲得良好的液晶配向膜，而且液晶配向劑的黏性增大而造成塗布特性降低。The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, and the like. It is preferably in the range of 1% by weight to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described later, and is preferably heated to form a coating film as a liquid crystal alignment film or a coating film to be a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small, and it is difficult to obtain a favorable liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, and it is difficult to obtain a favorable liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases to cause a decrease in coating properties.

特別優選的固形物濃度的範圍因將液晶配向劑塗布於基板上時所使用的方法而異。例如，於利用旋塗法的情況時，特別優選固形物濃度為1.5重量%~4.5重量%的範圍。於利用印刷法的情況時，特別優選使固形物濃度為3重量%~9重量%的範圍，由此而使溶液黏度成為12 mPa．s~50 mPa．s的範圍。於利用噴墨法的情況時，特別優選使固形物濃度為1重量%~5重量%的範圍，由此而使溶液黏 度成為3 mPa．s~15 mPa．s的範圍。A particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal alignment agent is applied onto the substrate. For example, in the case of using the spin coating method, the solid content concentration is particularly preferably in the range of 1.5% by weight to 4.5% by weight. In the case of using the printing method, it is particularly preferable to set the solid content to a range of 3% by weight to 9% by weight, thereby making the solution viscosity 12 mPa. s~50 mPa. The scope of s. In the case of using the inkjet method, it is particularly preferable to make the solid content concentration in the range of 1% by weight to 5% by weight, thereby making the solution sticky. Degree becomes 3 mPa. s~15 mPa. The scope of s.

調製本發明的液晶配向劑時的溫度優選為10℃~50℃，更優選為20℃~30℃。The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 10 ° C to 50 ° C, and more preferably from 20 ° C to 30 ° C.

<液晶配向膜及液晶顯示元件><Liquid alignment film and liquid crystal display element>

本發明的液晶配向膜由上述液晶配向劑而形成。而且，本發明的液晶顯示元件包含使用上述的液晶配向劑而形成的液晶配向膜。本發明的液晶顯示元件的運行模式並無特別限定，例如可適用於IPS型、TN型、STN型、FFS型、VA型、OCB型等各種驅動方式中。The liquid crystal alignment film of the present invention is formed of the above liquid crystal alignment agent. Further, the liquid crystal display element of the present invention comprises a liquid crystal alignment film formed using the above liquid crystal alignment agent. The operation mode of the liquid crystal display device of the present invention is not particularly limited, and can be applied to, for example, various driving methods such as IPS type, TN type, STN type, FFS type, VA type, and OCB type.

本發明的液晶顯示元件例如可通過以下的(1)~(3)的步驟而製造。步驟(1)根據所期望的運行模式而使用不同的基板。步驟(2)及步驟(3)通用於各運行模式中。The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). Step (1) uses different substrates depending on the desired mode of operation. Step (2) and step (3) are common to each operation mode.

[步驟(1)：塗膜的形成][Step (1): Formation of coating film]

首先，在基板上塗布本發明的液晶配向劑，其次對塗布面進行加熱而在基板上形成塗膜。First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate.

(1-1)例如於製造TN型、STN型或VA型液晶顯示元件的情況下，首先將二枚設有經圖案化的透明導電膜的基板作為一對，優選利用膠版印刷法、旋塗法、輥塗布機(roll coater)法或噴墨印刷法將本發明的液晶配向劑分別塗布於其各透明性導電膜形成面上。此處，基板例如可使用浮法玻璃、鈉玻璃等玻璃；包含聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚碸、聚碳酸酯、聚(脂環族烯烴)等塑料的透明基板。作為於基板的一個面所設的透明導電膜，可使用包含氧化錫(SnO₂ )的NESA膜(美國PPG公 司的注冊商標)、包含氧化銦-氧化錫(In₂ O₃ -SnO₂ )的ITO膜等。為了獲得圖案化的透明導電膜，例如可利用如下的方法：於形成無圖案的透明導電膜以後，利用光蝕刻而形成圖案的方法；於形成透明導電膜時使用具有所期望的圖案的掩模的方法等。於塗布液晶配向劑時，為了使基板表面及透明導電膜與塗膜的接著性變得更良好，亦可對基板表面中的需形成塗膜的面實施預先塗布官能性矽烷化合物、官能性鈦化合物等的預處理。(1-1) For example, in the case of manufacturing a TN type, STN type or VA type liquid crystal display element, first, two substrates each provided with a patterned transparent conductive film are used as a pair, preferably by offset printing or spin coating. The liquid crystal alignment agent of the present invention is applied to each of the transparent conductive film forming faces by a roll coater method or an inkjet printing method. Here, as the substrate, for example, glass such as float glass or soda glass may be used; and polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly(alicyclic olefin) may be used. A transparent substrate such as plastic. As the transparent conductive film provided on one surface of the substrate, a NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA) and indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) may be used. ITO film, etc. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photolithography after forming a non-patterned transparent conductive film, and a mask having a desired pattern when forming a transparent conductive film can be used. Method etc. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, the surface of the substrate on which the coating film is to be formed may be coated with a functional decane compound or a functional titanium. Pretreatment of compounds and the like.

於塗布液晶配向劑後，為了防止所塗布的配向劑流掛等，優選實施預熱(預焙)。預焙溫度優選為30℃~200℃，更優選為40℃~150℃，特別優選為40℃~100℃。預焙時間優選為0.25分鐘~10分鐘，更優選為0.5分鐘~5分鐘。其後，將溶劑完全除去，視需要以對聚合物中所存在的醯胺酸結構進行熱醯亞胺化為目的而實施煅燒(後烘)步驟。此時的煅燒溫度(後烘溫度)優選為80℃~300℃，更優選為120℃~250℃。後烘時間優選為5分鐘~200分鐘，更優選為10分鐘~100分鐘。如上所述而形成的膜的膜厚優選為0.001 μm~1 μm，更優選為0.005 μm~0.5 μm。After coating the liquid crystal alignment agent, it is preferred to carry out preheating (prebaking) in order to prevent the applied alignment agent from sagging or the like. The prebaking temperature is preferably from 30 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C, and particularly preferably from 40 ° C to 100 ° C. The prebaking time is preferably from 0.25 minutes to 10 minutes, more preferably from 0.5 minutes to 5 minutes. Thereafter, the solvent is completely removed, and if necessary, a calcination (post-baking) step is carried out for the purpose of thermally imidating the proline structure present in the polymer. The calcination temperature (post-baking temperature) at this time is preferably 80 ° C to 300 ° C, and more preferably 120 ° C to 250 ° C. The post-baking time is preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 100 minutes. The film thickness of the film formed as described above is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

(1-2)於製造IPS型液晶顯示元件的情況時，將本發明的液晶配向劑分別塗布於設有圖案化為梳齒型的透明導電膜的基板的導電膜形成面上、與並未設有導電膜的對向基板的一面上，其次對各塗布面進行加熱，由此而形成塗膜。關於此時所使用的基板及透明導電膜的材質、塗布方法、塗布後的加熱條件、透明導電膜的圖案化方法、基板 的預處理以及所形成的塗膜的優選膜厚，與上述(1-1)相同。(1-2) When manufacturing an IPS type liquid crystal display device, the liquid crystal alignment agent of the present invention is applied to a conductive film formation surface of a substrate provided with a pattern of a comb-shaped transparent conductive film, respectively On one surface of the counter substrate provided with the conductive film, the coated surfaces are heated next to form a coating film. Material of the substrate and the transparent conductive film used at this time, a coating method, heating conditions after coating, a patterning method of the transparent conductive film, and a substrate The pretreatment and the preferred film thickness of the formed coating film are the same as those of the above (1-1).

於上述(1-1)及(1-2)的任意情況時，均是將液晶配向劑塗布於基板上，然後除去有機溶劑而形成成為配向膜的塗膜。此時，本發明的液晶配向劑中所含有的聚合物為聚醯胺酸或者具有醯亞胺環結構與醯胺酸結構的醯亞胺化聚合物的情況時，亦可在塗膜形成後進一步進行加熱，藉此進行脫水閉環反應，而製成更進一步醯亞胺化的塗膜。In any of the above (1-1) and (1-2), the liquid crystal alignment agent is applied onto the substrate, and then the organic solvent is removed to form a coating film which becomes an alignment film. In this case, when the polymer contained in the liquid crystal alignment agent of the present invention is a polyphthalic acid or a ruthenium iodide polymer having a quinone ring structure and a phthalic acid structure, it may be formed after the coating film is formed. Further, heating is carried out to carry out a dehydration ring-closure reaction, thereby producing a coating film which is further imidized.

[步驟(2)：摩擦處理][Step (2): Friction treatment]

在製造TN型、STN型或IPS型液晶顯示元件的情況時，實施如下的摩擦處理：利用捲繞有布(所述布包含例如尼龍、人造絲、棉等纖維)的輥，於固定方向上對上述步驟(1)中所形成的塗膜實施摩擦處理。由此而對塗膜賦予液晶分子的配向能力，從而成為液晶配向膜。In the case of manufacturing a TN type, STN type or IPS type liquid crystal display element, the following rubbing treatment is carried out: in a fixed direction by using a roll wound with a cloth (the cloth contains fibers such as nylon, rayon, cotton, etc.) The coating film formed in the above step (1) is subjected to a rubbing treatment. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film, thereby becoming a liquid crystal alignment film.

另一方面，在製造VA型液晶顯示元件的情況時，可將上述步驟(1)中所形成的塗膜直接用作液晶配向膜，亦可對該塗膜實施摩擦處理。On the other hand, in the case of manufacturing a VA liquid crystal display element, the coating film formed in the above step (1) can be directly used as a liquid crystal alignment film, and the coating film can be subjected to a rubbing treatment.

亦可對如上所述而形成的液晶配向膜進一步進行如下的處理，從而使液晶配向膜具有於每個區域中不同的液晶配向能力：通過對液晶配向膜的一部分照射紫外線而使液晶配向膜的一部分區域的預傾角變化的處理；或者於液晶配向膜表面的一部分上形成抗蝕膜以後，於與先前的摩擦處理不同的方向上進行摩擦處理，然後除去抗蝕膜的處理。在此種情況時，可改善所得的液晶顯示元件的視野特 性。The liquid crystal alignment film formed as described above may be further subjected to the following treatment so that the liquid crystal alignment film has different liquid crystal alignment ability in each region: the liquid crystal alignment film is made by irradiating a part of the liquid crystal alignment film with ultraviolet rays. The treatment of the pretilt angle change of a part of the area; or after the resist film is formed on a part of the surface of the liquid crystal alignment film, the rubbing treatment is performed in a direction different from the previous rubbing treatment, and then the treatment of the resist film is removed. In this case, the field of view of the resulting liquid crystal display element can be improved. Sex.

另外，適於VA型的液晶顯示元件的液晶配向膜亦可適宜地用於聚合物穩定配向(Polymer sustained alignment，PSA)型液晶顯示元件中。Further, a liquid crystal alignment film suitable for a VA type liquid crystal display element can also be suitably used in a polymer sustained alignment (PSA) type liquid crystal display element.

[步驟(3)：液晶單元的構築][Step (3): Construction of liquid crystal cell]

對於如上所述而形成有液晶配向膜的一對基板，以二枚基板的液晶配向膜的摩擦方向成為正交或反平行的方式隔著間隙(單元間隙(cell gap))而對向配置，使用密封(seal)劑而貼合二枚基板的周邊部，於由基板表面及密封劑而劃分的單元間隙內注入填充液晶後，對注入孔進行密封而構成液晶單元。其次，將偏光板以其偏光方向與各基板上所形成的液晶配向膜的摩擦方向一致或正交的方式貼合於液晶單元的外表面上，由此可獲得液晶顯示元件。In the pair of substrates on which the liquid crystal alignment film is formed as described above, the rubbing directions of the liquid crystal alignment films of the two substrates are arranged to face each other with a gap (cell gap) so as to be orthogonal or anti-parallel. The peripheral portion of the two substrates is bonded by a sealant, and the filling liquid crystal is injected into the cell gap defined by the surface of the substrate and the sealant, and then the injection hole is sealed to constitute a liquid crystal cell. Then, the polarizing plate is bonded to the outer surface of the liquid crystal cell such that the polarizing direction thereof is aligned or orthogonal to the rubbing direction of the liquid crystal alignment film formed on each of the substrates, whereby a liquid crystal display element can be obtained.

密封劑例如可使用含有硬化劑及作為間隔物的氧化鋁球的環氧樹脂等。As the sealant, for example, an epoxy resin containing a curing agent and an alumina ball as a spacer can be used.

液晶可列舉向列型(nematic)液晶及層列型(smectic)液晶，其中優選向列型液晶，例如可使用席夫鹼(Schiff base)類液晶、氧化偶氮類液晶、聯苯類液晶、苯基環己烷類液晶、酯類液晶、三聯苯類液晶、聯苯基環己烷類液晶、嘧啶類液晶、二噁烷類液晶、雙環辛烷類液晶、立方烷類液晶等。而且，於該些液晶中例如亦可添加如下化合物而使用：、膽甾醇壬酸酯、膽甾醇碳酸酯等膽甾醇型液晶；作為商品名“C-15”、“CB-15”(默克公司製造)而市售的旋光劑(chiral agent)；對癸 氧基苯亞甲基-對胺基-2-甲基丁基肉桂酸酯等鐵電液晶等。Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, or the like can be used. Phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal or the like. Further, for the liquid crystals, for example, the following compounds may be added and used: a cholesteric liquid crystal such as cholesteryl phthalate or cholesteryl carbonate; a chiral agent commercially available as "C-15" or "CB-15" (manufactured by Merck); A ferroelectric liquid crystal such as oxybenzylidene-p-amino-2-methylbutylcinnamate.

作為貼合於液晶單元的外表面的偏光板，可列舉以乙酸纖維素保護膜夾持被稱為“H膜”的偏光膜(所述H膜是一面使聚乙烯醇延伸配向一面吸收碘而成的偏光膜)而成的偏光板或包含H膜自身的偏光板。The polarizing plate to be bonded to the outer surface of the liquid crystal cell may be a polarizing film called "H film" sandwiched between a cellulose acetate protective film (the H film is one surface in which polyvinyl alcohol is stretched to absorb iodine on one side). A polarizing film formed of a polarizing film or a polarizing plate including the H film itself.

本發明的液晶顯示元件亦可包含相位差膜，所述相位差膜包含相位差膜用液晶配向膜作為使用本發明的液晶配向劑而形成的液晶配向膜。在這種情況下，本發明的液晶顯示元件可於背面側(背光源側)偏光板與液晶單元之間包含該相位差膜，亦可於視認側偏光板與液晶單元之間包含該相位差膜，或者於其雙方包含該相位差膜。此種相位差膜例如可通過如下方式而製造：將本發明的液晶配向劑塗布於乙酸纖維素保護膜或偏光膜等基板上而形成塗膜，其次視需要實施摩擦處理而製成相位差膜用液晶配向膜，然後於該膜的表面上塗布聚合性液晶而使其硬化。The liquid crystal display device of the present invention may further include a retardation film containing a liquid crystal alignment film for a retardation film as a liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention. In this case, the liquid crystal display device of the present invention may include the retardation film between the polarizing plate on the back side (backlight side) and the liquid crystal cell, or may include the phase difference between the polarizing plate and the liquid crystal cell. The film or the retardation film is contained on both sides thereof. Such a retardation film can be produced, for example, by applying the liquid crystal alignment agent of the present invention to a substrate such as a cellulose acetate protective film or a polarizing film to form a coating film, and secondarily performing a rubbing treatment to form a retardation film. A liquid crystal alignment film is used, and then a polymerizable liquid crystal is applied onto the surface of the film to be cured.

本發明的液晶顯示元件可有效地適用於各種裝置中，例如可用於時鐘、攜帯型遊戲機、文字處理機、筆記本電腦、汽車導航系統、可攜式攝像機、個人數字助理(Personal Digital Assistant，PDA)、數位相機、手機、智慧型手機、各種顯示器、液晶電視、訊息顯示器等各種顯示裝置中。The liquid crystal display element of the present invention can be effectively applied to various devices, such as a clock, a portable game machine, a word processor, a notebook computer, a car navigation system, a camcorder, and a personal digital assistant (Personal Digital Assistant, PDA), digital cameras, mobile phones, smart phones, various displays, LCD TVs, message displays, and other display devices.

[實例][Example]

以下，通過實例對本發明加以更具體的說明，但本發明並不受該些實例限制。Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited by the examples.

合成例中的各聚合物溶液的溶液黏度及聚醯亞胺的醯亞胺化率可利用以下的方法而測定。The solution viscosity of each polymer solution in the synthesis example and the oxime imidization ratio of polyimine can be measured by the following methods.

[聚合物溶液的溶液黏度][Solid viscosity of polymer solution]

聚合物溶液的溶液黏度(mPa．s)可使用E型旋轉黏度計，於25℃下對使用規定的溶劑而將聚合物濃度調整為10重量%的溶液進行測定。The solution viscosity (mPa.s) of the polymer solution can be measured by using a T-type rotational viscometer at 25 ° C for a solution having a polymer concentration adjusted to 10% by weight using a predetermined solvent.

[聚醯亞胺的醯亞胺化率][醯Iminization rate of polyimine]

將聚醯亞胺溶液投入至純水中，於室溫下對所得的沉澱充分減壓乾燥後，溶解於氘化二甲基亞碸中，以四甲基矽烷為基準物質而於室溫下測定¹ H-NMR。根據所得的¹ H-NMR光譜，由下述數學式(1)所表示的式而求出醯亞胺化率[%]。The polyimide solution was put into pure water, at room temperature, the resulting precipitate was sufficiently dried under reduced pressure, dissolved in deuterated dimethyl sulfoxide, tetramethyl ^silane-1 as a reference substance measured at room temperature H-NMR. From the obtained ¹ H-NMR spectrum, the oxime imidization ratio [%] was determined from the formula represented by the following formula (1).

醯亞胺化率[%]=(1-A¹ /A² ×α)×100………(1)醯imination rate [%]=(1-A ¹ /A ² ×α)×100...(1)

於數學式(1)中，A¹ 是出現在化學位移10 ppm附近的源自NH基的質子的峰面積，A² 是源自其他質子的峰面積，α是其他質子相對於聚合物的前驅物(聚醯胺酸)中的NH基的1個質子的個數比例。In the formula (1), A ¹ is the peak area of the proton derived from the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of other protons relative to the polymer. The ratio of the number of protons of the NH group in the substance (polyproline).

<二胺的合成><Synthesis of diamine>

於以下的合成例中，視需要以下述的標度(scale)反復進行，由此而確保以後的聚合例的必需量。In the following synthesis examples, the following scales are repeated as necessary, thereby ensuring the necessary amount of the subsequent polymerization examples.

[合成例1：化合物(a-1-1)的合成][Synthesis Example 1: Synthesis of Compound (a-1-1)]

依照下述流程1而合成下述式(A-1-1)所表示的化 合物(a-1-1)。The chemical represented by the following formula (A-1-1) is synthesized according to the following Scheme 1. Compound (a-1-1).

於具有攪拌機、氮氣導入管及溫度計的1 L三口燒瓶中，將4-氟硝基苯31 g、4-胺基哌啶10 g、碳酸氫鈉18.5 g、乙醇200 mL加以混合，於80℃下攪拌4小時。反應結束後，使其溶解於乙酸乙酯中而以蒸餾水進行分液清洗。繼而，用硫酸鎂使有機層乾燥後進行濃縮，用乙醇對所得的固體加以清洗而獲得化合物(a-1)的結晶26 g。其次，於氮氣環境下，於1 L三口燒瓶中將化合物(a-1)25 g、鋅99 g、氯化銨16 g、四氫呋喃(Tetra Hydro Furan，THF)300 mL、乙醇50 mL加以混合，於冰浴中一面進行攪拌一面滴加蒸餾水40 mL，然後於20℃下進行4小時的攪拌。通過過濾將鋅等除去後，使其溶解於乙酸乙酯中，用蒸餾水進行分液清洗。繼而，用硫酸鎂對有機層進行乾燥後進行濃縮，獲得褐色粉末。用乙酸乙酯100 mL、己烷200 mL進行再結晶，獲得下述式(A-1-1)所表示的化合物(a-1-1)的結晶17 g。Mixing 4-fluoronitrobenzene 31 g, 4-aminopiperidine 10 g, sodium bicarbonate 18.5 g, and ethanol 200 mL in a 1 L three-necked flask equipped with a stirrer, a nitrogen gas introduction tube, and a thermometer at 80 ° C Stir under 4 hours. After completion of the reaction, it was dissolved in ethyl acetate and washed with distilled water. Then, the organic layer was dried over magnesium sulfate, concentrated, and the obtained solid was washed with ethanol to obtain 26 g of the crystal of compound (a-1). Next, 25 g of compound (a-1), 99 g of zinc, 16 g of ammonium chloride, 300 mL of tetrahydrofuran (Tetra Hydro Furan, THF), and 50 mL of ethanol were mixed in a 1 L three-necked flask under a nitrogen atmosphere. While stirring in an ice bath, 40 mL of distilled water was added dropwise, followed by stirring at 20 ° C for 4 hours. After removing zinc or the like by filtration, it was dissolved in ethyl acetate, and the mixture was washed with distilled water. Then, the organic layer was dried over magnesium sulfate and concentrated to give a brown powder. Recrystallization was carried out by using 100 mL of ethyl acetate and 200 mL of hexane to obtain 17 g of a crystal of the compound (a-1-1) represented by the following formula (A-1-1).

[合成例2：化合物(a-1-3)的合成][Synthesis Example 2: Synthesis of Compound (a-1-3)]

依照下述流程2而合成下述式(A-1-3)所表示的化合物(a-1-3)。The compound (a-1-3) represented by the following formula (A-1-3) was synthesized according to the following Scheme 2.

於具有攪拌機、氮氣導入管及溫度計的1 L三口燒瓶中，將4-氟硝基苯15.5 g、4-羥基哌啶10 g、碳酸氫鈉9.2 g、乙醇100 mL加以混合，於80℃下進行5小時的攪拌。反應結束後，使其溶解於乙酸乙酯中而以蒸餾水進行分液清洗。用硫酸鎂使有機層乾燥後進行濃縮，用乙醇對所得的固體進行再結晶而獲得化合物(a-2)的結晶20 g。其次，於氮氣環境下，於500 mL三口燒瓶中將化合物(a-2)19 g、三乙胺13 g、THF 150 mL加以混合，於冰浴中一面進行攪拌一面滴加於THF 50 mL中溶解有4-硝基苯甲醯氯16 g者，然後於20℃下進行1小時的攪拌。反應結束後，使其溶解於乙酸乙酯中而用蒸餾水進行分液清洗。用硫酸鎂使有機層乾燥後進行濃縮，用乙醇對所得的固體進行再結晶，獲得化合物(a-3)的結晶25 g。最後，於氮氣環境下， 於500 mL三口燒瓶中將化合物(a-3)24.5 g、鋅87 g、氯化銨14 g、THF 300 mL、乙醇50 mL加以混合，於冰浴中一面進行攪拌一面滴加蒸餾水35 mL，然後於20℃下進行5小時的攪拌。通過過濾將鋅等除去後，使其溶解於乙酸乙酯中，用蒸餾水進行分液清洗。將用硫酸鎂對有機層進行乾燥後進行濃縮而所得的粉末於乙酸乙酯100 mL、己烷200 mL中進行再結晶，獲得化合物(a-1-3)的結晶19 g。Mixing 4-fluoronitrobenzene 15.5 g, 4-hydroxypiperidine 10 g, sodium hydrogencarbonate 9.2 g, and ethanol 100 mL in a 1 L three-necked flask equipped with a stirrer, a nitrogen gas introduction tube, and a thermometer at 80 ° C Stir for 5 hours. After completion of the reaction, it was dissolved in ethyl acetate and washed with distilled water. The organic layer was dried over magnesium sulfate, concentrated, and the obtained solid was recrystallized from ethanol to obtain 20 g of crystals of compound (a-2). Next, 19 g of the compound (a-2), 13 g of triethylamine, and 150 mL of THF were mixed in a 500 mL three-necked flask under a nitrogen atmosphere, and added dropwise to the THF 50 mL while stirring in an ice bath. Dissolved with 16 g of 4-nitrobenzidine chloride, and then stirred at 20 ° C for 1 hour. After completion of the reaction, the mixture was dissolved in ethyl acetate and washed with distilled water. The organic layer was dried over magnesium sulfate, concentrated, and the obtained solid was recrystallized from ethanol to obtain 25 g of crystals of compound (a-3). Finally, under a nitrogen atmosphere, In a 500 mL three-necked flask, 24.5 g of the compound (a-3), 87 g of zinc, 14 g of ammonium chloride, 300 mL of THF, and 50 mL of ethanol were mixed, and 35 mL of distilled water was added dropwise while stirring in an ice bath. Then, stirring was carried out for 5 hours at 20 °C. After removing zinc or the like by filtration, it was dissolved in ethyl acetate, and the mixture was washed with distilled water. The organic layer was dried over magnesium sulfate and concentrated, and the obtained powder was recrystallized from ethyl acetate (100 mL) and hexane (200 mL) to obtain 19 g of the compound (a-1-3).

[合成例3：化合物(a-1-5)的合成][Synthesis Example 3: Synthesis of Compound (a-1-5)]

依照下述流程3而合成下述式(A-1-5)所表示的化合物(a-1-5)。The compound (a-1-5) represented by the following formula (A-1-5) was synthesized according to the following Scheme 3.

於具有攪拌機、氮氣導入管及溫度計的1 L三口燒瓶中，將4-氟硝基苯31 g、氟化銫36 g、異哌啶酸(isonipecotic acid)26 g、二甲基亞碸200 mL加以混合，於110℃下進行3小時的攪拌。反應結束後，混合蒸餾水400 mL，通過過濾而回收所析出的粉末。用蒸餾水、己烷進行充分清洗， 加以乾燥而獲得化合物(a-4)44 g。其次，將化合物(a-4)25 g、4-硝基苯酚13 g、1-(3-二甲基胺基丙基)-3-乙基碳二醯亞胺鹽酸鹽(EDC)23 g、THF 350 mL加以混合，於冰浴中一面攪拌一面添加二甲胺基吡啶2.5 g，然後於20℃下進行4小時的攪拌。反應結束後，使其溶解於乙酸乙酯中，用蒸餾水進行分液操作。用硫酸鎂使有機層乾燥後進行濃縮，用乙醇對所得的固體進行清洗，獲得化合物(a-5)的結晶24 g。最後，於500 mL三口燒瓶中，於氮氣環境下將化合物(a-5)24 g、鋅85 g、氯化銨14 g、THF 300 mL、乙醇50 mL加以混合，於冰浴中一面攪拌一面滴加蒸餾水35 mL，然後於20℃下進行5小時的攪拌。通過過濾將鋅等除去後，使其溶解於乙酸乙酯中，用蒸餾水進行分液清洗。用硫酸鎂使有機層乾燥後進行濃縮，使所得的粉末再溶解於THF中而進行矽藻土過濾。對濾液進行濃縮而獲得化合物(a-1-5)的粉末16 g。In a 1 L three-necked flask equipped with a stirrer, a nitrogen inlet tube, and a thermometer, 31 g of 4-fluoronitrobenzene, 36 g of cesium fluoride, 26 g of isepipenic acid, and 200 mL of dimethyl hydrazine. The mixture was mixed and stirred at 110 ° C for 3 hours. After completion of the reaction, 400 mL of distilled water was mixed, and the precipitated powder was collected by filtration. Wash thoroughly with distilled water and hexane. It was dried to obtain 44 g of the compound (a-4). Next, 25 g of the compound (a-4), 13 g of 4-nitrophenol, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) 23 g, THF 350 mL were mixed, and 2.5 g of dimethylaminopyridine was added while stirring in an ice bath, followed by stirring at 20 ° C for 4 hours. After completion of the reaction, it was dissolved in ethyl acetate, and the liquid separation operation was carried out with distilled water. The organic layer was dried over magnesium sulfate, concentrated, and the obtained solid was washed with ethanol to obtain 24 g of crystals of compound (a-5). Finally, in a 500 mL three-necked flask, 24 g of compound (a-5), 85 g of zinc, 14 g of ammonium chloride, 300 mL of THF, and 50 mL of ethanol were mixed under a nitrogen atmosphere, and the mixture was stirred while stirring in an ice bath. 35 mL of distilled water was added dropwise, followed by stirring at 20 ° C for 5 hours. After removing zinc or the like by filtration, it was dissolved in ethyl acetate, and the mixture was washed with distilled water. The organic layer was dried over magnesium sulfate, concentrated, and the obtained powder was redissolved in THF and filtered over Celite. The filtrate was concentrated to obtain 16 g of a powder of the compound (a-1-5).

[合成例4：化合物(a-1-6)的合成][Synthesis Example 4: Synthesis of Compound (a-1-6)]

依照下述流程4而合成下述(A-1-6)所表示的化合物(a-1-6)。The compound (a-1-6) represented by the following (A-1-6) was synthesized according to the following Scheme 4.

[化11] [11]

將通過與合成例3相同的方法而獲得的化合物(a-4)15 g、3-硝基苯酚8.35 g、1-(3-二甲基胺基丙基)-3-乙基碳二醯亞胺鹽酸鹽(EDC)13.8 g、THF 180 mL加以混合，於冰浴中一面攪拌一面添加二甲胺基吡啶1.47 g後，於20℃下進行6小時的攪拌。反應結束後，使其溶解於乙酸乙酯中，用蒸餾水進行分液操作。用硫酸鎂使有機層乾燥，用乙醇對所得的固體進行清洗，獲得化合物(a-6)的結晶17.9 g。最後，於500 mL三口燒瓶中，於氮氣環境下將化合物(a-6)17.9 g、鋅63.2 g、氯化銨10.3 g、THF 210 mL、乙醇30 mL加以混合，於冰浴中一面攪拌一面滴加蒸餾水24 mL，然後於20℃下進行7小時的攪拌。通過過濾將鋅等除去後，使其溶解於乙酸乙酯中，用蒸餾水進行分液清洗。用硫酸鎂使有機層乾燥後加以濃縮，將所得的粉末再溶解於THF中而進行矽藻土過濾。對濾液進行濃縮，將所得的固體於THF、己烷中進行再結晶，獲得化合物(a-1-6)13 g。15 g of the compound (a-4) obtained by the same method as in Synthesis Example 3, 3-nitrophenol 8.35 g, 1-(3-dimethylaminopropyl)-3-ethylcarbazide 13.8 g of imine hydrochloride (EDC) and 180 mL of THF were mixed, and 1.47 g of dimethylaminopyridine was added thereto while stirring in an ice bath, followed by stirring at 20 ° C for 6 hours. After completion of the reaction, it was dissolved in ethyl acetate, and the liquid separation operation was carried out with distilled water. The organic layer was dried over magnesium sulfate, and the obtained solid was washed with ethanol to obtain 17.9 g of crystals of compound (a-6). Finally, in a 500 mL three-necked flask, compound (a-6) 17.9 g, zinc 63.2 g, ammonium chloride 10.3 g, THF 210 mL, and ethanol 30 mL were mixed under a nitrogen atmosphere, and the mixture was stirred while stirring in an ice bath. 24 mL of distilled water was added dropwise, followed by stirring at 20 ° C for 7 hours. After removing zinc or the like by filtration, it was dissolved in ethyl acetate, and the mixture was washed with distilled water. The organic layer was dried over magnesium sulfate and concentrated, and the obtained powder was redissolved in THF and filtered over Celite. The filtrate was concentrated, and the obtained solid was recrystallized from THF and hexane to obtain 13 g of compound (a-1-6).

<聚醯亞胺的合成><Synthesis of Polyimine> [聚合例1][Polymer Example 1]

將作為四羧酸二酐的2,3,5-三羧基環戊基乙酸二酐(TCA)0.5莫耳(11.2 g)、作為二胺的3,5-二胺基苯甲酸膽甾烷基酯0.1莫耳(52.3 g)、膽甾烷基氧基-2,4-二胺基苯0.05莫耳(24.8 g)、化合物(a-1-5)0.025莫耳(0.78 g)、及對苯二胺0.325莫耳(3.5 g)溶解於N-甲基-2-吡咯烷酮(NMP)56 g中，於60℃下進行6小時反應，由此而獲得含有20重量%聚醯胺酸的溶液。分取少量該溶液，加入N-甲基-2-吡咯烷酮而製成聚醯胺酸濃度為10重量%的溶液，於25℃下測定的溶液黏度為60 mPa．s。2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as a tetracarboxylic dianhydride 0.5 mol (11.2 g), 3,5-diaminobenzoic acid cholesteryl as a diamine Ester 0.1 mol (52.3 g), cholestyloxy-2,4-diaminobenzene 0.05 mol (24.8 g), compound (a-1-5) 0.025 mol (0.78 g), and The phenylenediamine 0.325 mol (3.5 g) was dissolved in 56 g of N-methyl-2-pyrrolidone (NMP), and reacted at 60 ° C for 6 hours, thereby obtaining a solution containing 20% by weight of polyglycine. . A small amount of this solution was added, and N-methyl-2-pyrrolidone was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity at 25 ° C was 60 mPa. s.

其次，於所得的聚醯胺酸溶液中追加NMP 130 g，添加吡啶2.4 g及乙酸酐3.1 g而於110℃下進行4小時的脫水閉環反應。於脫水閉環反應後，用新的NMP對系統內的溶劑進行溶劑置換(通過該溶劑置換操作而將脫水閉環反應中所使用的吡啶及乙酸酐除去至系統外。下同)，由此獲得含有20重量%的醯亞胺化率為46%的聚醯亞胺(PI-1)的溶液。分取少量該溶液而加入NMP，製成聚醯亞胺濃度為10重量%的溶液，於25℃下測定的溶液黏度為55 mPa．s。Next, 130 g of NMP was added to the obtained polyamic acid solution, and 2.4 g of pyridine and 3.1 g of acetic anhydride were added to carry out a dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system is subjected to solvent replacement with a new NMP (by the solvent replacement operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system. The same applies hereinafter), thereby obtaining a content. 20% by weight of a solution of polyamidolimine (PI-1) having a ruthenium iodide ratio of 46%. A small amount of this solution was added and NMP was added to prepare a solution having a polyamidene concentration of 10% by weight, and the solution viscosity at 25 ° C was 55 mPa. s.

[聚合例2~聚合例9、比較聚合例1、比較聚合例2][Polymerization Example 2 to Polymerization Example 9, Comparative Polymerization Example 1, Comparative Polymerization Example 2]

除了如下述表1所示那樣變更所使用的四羧酸二酐及二胺的種類及量的方面、如下述表1所示那樣變更所使用的吡啶及乙酸酐的量的方面以外，通過與上述聚合例1同 樣的方法而分別合成聚醯亞胺(PI-2)~聚醯亞胺(PI-11)。另外，以四羧酸二酐及二胺的合計量相對於反應溶液的總量而言成為20重量%的方式加入NMP而調製反應溶液。In addition to the type and amount of the tetracarboxylic dianhydride and the diamine to be used, as shown in the following Table 1, the amount of pyridine and acetic anhydride to be used is changed as shown in Table 1 below. The above polymerization example 1 is the same Polyimine (PI-2) ~ polyimine (PI-11) was synthesized by the same method. In addition, NMP was added so that the total amount of the tetracarboxylic dianhydride and the diamine was 20% by weight based on the total amount of the reaction solution, and the reaction solution was prepared.

<聚醯胺酸的合成><Synthesis of polylysine> [聚合例10][Polymer Example 10]

將作為四羧酸二酐的1,2,3,4-環丁烷四羧酸二酐0.45莫耳(5.6 g)及1,2,4,5-苯四羧酸二酐0.05莫耳(0.7 g)、作為二胺的化合物(a-1-5)0.1莫耳(2.0 g)、十四烷氧基-2,4-二胺基苯0.05莫耳(1.0 g)、3,6-雙(4-胺基苯甲醯氧基)膽甾烷0.01莫耳(0.4 g)、4-胺基苯基-4'-胺基苯甲酸酯0.29莫耳(4.2 g)、及4,4'-[4,4'-丙烷-1,3-二基雙(哌啶-1,4-二基)]二苯胺0.05莫耳(1.2 g)溶解於NMP 85 g中，於40℃下進行8小時的反應，由此而獲得含有15重量%聚醯胺酸的溶液。分取少量該溶液，加入NMP而製成聚醯胺酸濃度為10重量%的溶液，於25℃下所測定的溶液黏度為80 mPa‧s。0.45 mol (5.6 g) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 0.05 mol of 1,2,4,5-benzenetetracarboxylic dianhydride ( 0.7 g), as a diamine compound (a-1-5) 0.1 mol (2.0 g), tetradecyloxy-2,4-diaminobenzene 0.05 mol (1.0 g), 3,6- Bis(4-aminobenzylideneoxy)cholesterane 0.01 mol (0.4 g), 4-aminophenyl-4'-aminobenzoate 0.29 mol (4.2 g), and 4, 4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine 0.05 mol (1.2 g) was dissolved in NMP 85 g at 40 ° C The reaction was carried out for 8 hours, whereby a solution containing 15% by weight of polyamic acid was obtained. A small amount of this solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the solution viscosity measured at 25 ° C was 80 mPa ‧ s.

[聚合例11~聚合例17、比較聚合例3][Polymerization Example 11 to Polymerization Example 17, Comparative Polymerization Example 3]

如下述表2所示那樣變更所使用的四羧酸二酐及二胺的種類及量，除此以外通過與上述聚合例10同樣的方法而分別合成聚醯胺酸(PA-2)~聚醯胺酸(PA-9)。另外，以四羧酸二酐及二胺的合計量相對於反應溶液的總量而言成為15重量%的方式加入NMP而調製反應溶液。The polyglycine (PA-2)-poly was synthesized by the same method as the above-mentioned polymerization example 10 except that the type and amount of the tetracarboxylic dianhydride and the diamine used were changed as shown in the following Table 2. Proline (PA-9). In addition, NMP was added so that the total amount of the tetracarboxylic dianhydride and the diamine was 15% by weight based on the total amount of the reaction solution, and the reaction solution was prepared.

於表1及表2中，四羧酸二酐的數值表示相對於合成中所使用的四羧酸二酐的總量的含有比例[mol%]，二胺的數值表示相對於合成中所使用的二胺的總量的含有比例[mol%]。吡啶及乙酸酐的數值表示相對於聚醯胺酸所具有的醯胺酸單元數的含有比例[mol%]。In Tables 1 and 2, the numerical value of the tetracarboxylic dianhydride indicates the content ratio [mol%] with respect to the total amount of the tetracarboxylic dianhydride used in the synthesis, and the numerical value of the diamine is used relative to the synthesis. The content ratio of the total amount of the diamine [mol%]. The numerical values of pyridine and acetic anhydride indicate the content ratio [mol%] of the number of methionine units which the polyphthalic acid has.

四羧酸二酐及二胺的略稱分別為以下的含義。The abbreviations of tetracarboxylic dianhydride and diamine are respectively the following meanings.

<四羧酸二酐><tetracarboxylic dianhydride>

J：2,3,5-三羧基環戊基乙酸二酐J: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

K：1,2,3,4-環丁烷四羧酸二酐K: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

L：1,2,4,5-苯四羧酸二酐L: 1,2,4,5-benzenetetracarboxylic dianhydride

<二胺><Diamine>

B：3,5-二胺基苯甲酸膽甾烷基酯B: cholesteryl 3,5-diaminobenzoate

C：膽甾烷基氧基-2,4-二胺基苯C: cholesteryloxy-2,4-diaminobenzene

D：對苯二胺D: p-phenylenediamine

E：3,5-二胺基苯甲酸E: 3,5-diaminobenzoic acid

F：十四烷氧基-2,4-二胺基苯F: tetradecyloxy-2,4-diaminobenzene

G：3,6-雙(4-胺基苯甲醯氧基)膽甾烷G: 3,6-bis(4-aminobenzimidyloxy)cholestane

H：4-胺基苯基-4'-胺基苯甲酸酯H: 4-aminophenyl-4'-aminobenzoic acid ester

I：4,4'-[4,4'-丙烷-1,3-二基雙(哌啶-1,4-二基)]二苯胺I: 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine

<含有環氧基的化合物(EPS-1)的合成><Synthesis of epoxy group-containing compound (EPS-1)>

於具有攪拌機、溫度計、滴液漏斗及回流冷凝管的反應器中裝入2-(3,4-環氧基環己基)乙基三甲氧基矽烷34.48 g、甲基異丁基酮34.48 g及三乙胺3.45 g，於室溫下進行混合。其次，利用滴液漏斗以30分鐘而滴加去離子水27.59 g後，一面於回流下進行攪拌，一面於80℃下進行6小時的反應。於反應結束後，取出有機層，藉由0.2重量%的硝酸銨水溶液而清洗至清洗後的水成為中性後，於減壓下蒸餾除去溶劑及水，由此而獲得黏稠的聚有機矽氧烷溶液。對該聚有機矽氧烷進行¹ H-NMR分析，結果是於化學位移(σ)=3.2 ppm附近如理論強度那樣獲得基於環氧基的峰值，確認於反應中並不產生環氧基的副反應。該聚有機矽氧烷的重量平均分子量Mw為3,000、環氧當量為184.8 g/mol。a reactor equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 23.48 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane and 34.48 g of methyl isobutyl ketone. 3.45 g of triethylamine was mixed at room temperature. Next, 27.59 g of deionized water was added dropwise thereto over 30 minutes using a dropping funnel, and the mixture was stirred at reflux for 6 hours at 80 °C. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a viscous polyorganosiloxane. Alkane solution. The ¹ H-NMR analysis of the polyorganosiloxane was carried out, and as a result, a peak based on the epoxy group was obtained as the theoretical intensity in the vicinity of the chemical shift (σ) = 3.2 ppm, and it was confirmed that the epoxy group was not produced in the reaction. reaction. The polyorganosiloxane had a weight average molecular weight Mw of 3,000 and an epoxy equivalent of 184.8 g/mol.

於200 ml的三口燒瓶中裝入上述聚有機矽氧烷7.70 g、作為溶劑的甲基異丁基酮44.8 g、4'-戊基-1,1'-雙環己基-4-羧酸3.50 g及作為催化劑的四丁基溴化銨0.77 g，於100℃下進行8小時的攪拌下進行反應。於反應結束後，於反應混合物中加入乙酸乙酯而對所得的溶液進行3次水洗，使用硫酸鎂而將有機層乾燥後，蒸餾除去溶劑，由此獲得反應性聚有機矽氧烷(化合物(EPS-1))10.9 g。化合物 (EPS-1)的重量平均分子量Mw為8,500。A 200 ml three-necked flask was charged with 7.70 g of the above polyorganosiloxane, 44.8 g of methyl isobutyl ketone as a solvent, and 3.50 g of 4'-pentyl-1,1'-dicyclohexyl-4-carboxylic acid. And 0.77 g of tetrabutylammonium bromide as a catalyst, and the reaction was carried out under stirring at 100 ° C for 8 hours. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the obtained solution was washed with water three times. After drying the organic layer with magnesium sulfate, the solvent was evaporated to obtain a reactive polyorganooxane (compound ( EPS-1)) 10.9 g. Compound The weight average molecular weight Mw of (EPS-1) was 8,500.

<液晶配向劑的調製><Modulation of liquid crystal alignment agent> [實例1][Example 1] (1)印刷性評價用液晶配向劑的調製(1) Modulation of liquid crystal alignment agent for printability evaluation

於含有100重量份聚合例1中所得的聚醯亞胺(PI-1)的溶液中加入N-甲基-2-吡咯烷酮(NMP)及丁基溶纖劑(Butyl cellosolve，BC)，製成溶劑組成為NMP：BC=50：50(重量比)、固形物濃度為6.5重量%的溶液。使用孔徑為1 μm的過濾器而對該溶液進行過濾，由此而調製印刷性評價用液晶配向劑A。N-methyl-2-pyrrolidone (NMP) and Butyl cellosolve (BC) were added to a solution containing 100 parts by weight of the polyimine (PI-1) obtained in Polymerization Example 1 to prepare a solvent group. A solution having NMP: BC = 50:50 (weight ratio) and a solid concentration of 6.5% by weight. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent A for evaluation of printability.

(2)元件製造用液晶配向劑的調製(2) Modulation of liquid crystal alignment agent for component manufacturing

於上述(1)中，將過濾前的溶液的固形物濃度設為4.0重量%，除此以外與上述(1)同樣地進行調製而獲得元件製造用液晶配向劑B。In the above (1), the liquid crystal alignment agent B for element production was obtained in the same manner as in the above (1) except that the solid content of the solution before the filtration was changed to 4.0% by weight.

[實例2~實例26、比較例1~比較例9][Example 2 to Example 26, Comparative Example 1 to Comparative Example 9]

如下述表3及表4中所記載那樣變更所使用的聚合物、添加劑，除此以外利用與上述實例1同樣的方法而分別獲得印刷性評價用液晶配向劑A及元件製造用液晶配向劑B。The liquid crystal alignment agent A for the printability evaluation and the liquid crystal alignment agent B for the element production were respectively obtained by the same method as in the above-described Example 1 except that the polymer or the additive to be used was changed as described in the following Tables 3 and 4. .

<液晶顯示元件的製造><Manufacture of liquid crystal display element> [製造例1][Manufacturing Example 1]

使用旋轉器將上述所調製的實例1的元件製造用液晶配向劑B塗布於厚度為1 mm的設在玻璃基板的一個面上的包含ITO膜的透明導電膜上，於80℃的熱板上進行1 分鐘的加熱。其次，於230℃的熱板上進行30分鐘的加熱，由此而形成膜厚約80 nm的塗膜(液晶配向膜)。反復進行該操作而製造4枚(2對)具有液晶配向膜的基板。The liquid crystal alignment agent B for element production prepared in the above-described Example 1 was applied onto a transparent conductive film containing an ITO film provided on one surface of a glass substrate having a thickness of 1 mm on a hot plate at 80 ° C using a rotator. Carry out 1 Minutes of heating. Next, heating was performed on a hot plate at 230 ° C for 30 minutes to form a coating film (liquid crystal alignment film) having a film thickness of about 80 nm. This operation was repeated to produce four (two pairs) of substrates having a liquid crystal alignment film.

其次，對於具有液晶配向膜的一對基板，於具有液晶配向膜的面的各個外緣塗布放入有直徑為3.5 μm的氧化鋁球的環氧樹脂接著劑後，以各個液晶配向膜面相對的方式使其重疊而進行壓接，使接著劑硬化。其次，自液晶注入口而於一對基板間填充負型液晶(默克(Merck)公司製造、MLC-6608)後，用丙烯酸類光硬化接著劑將液晶注入口密封，於基板的外側的兩個面貼合偏光板，由此而製造垂直配向型液晶顯示元件。Next, for a pair of substrates having a liquid crystal alignment film, an epoxy resin adhesive having an alumina ball having a diameter of 3.5 μm is applied to each of the outer edges of the surface having the liquid crystal alignment film, and then the respective liquid crystal alignment film faces are opposed to each other. The way it is overlapped and crimped to harden the adhesive. Next, a negative liquid crystal (manufactured by Merck Co., Ltd., MLC-6608) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocuring adhesive, and the two sides of the substrate were sealed. The polarizing plate is attached to each other, whereby a vertical alignment type liquid crystal display element is manufactured.

[製造例2~製造例14、比較製造例1~比較製造例6][Production Example 2 to Production Example 14, Comparative Production Example 1 to Comparative Production Example 6]

將所使用的液晶配向劑變更為實例2~實例14或比較例1~比較例6的元件製造用液晶配向劑B，除此以外利用與上述製造例1同樣的方法而製造垂直配向型液晶顯示元件。The liquid crystal alignment agent to be used was changed to the liquid crystal alignment agent B for element production of the example 2 to the example 14 or the comparative example 1 to the comparative example 6, and the vertical alignment type liquid crystal display was produced by the same method as the above-mentioned production example 1. element.

[製造例15][Manufacturing Example 15]

使用旋轉器將上述所調製的實例15的元件製造用液晶配向劑B塗布於厚度為1 mm的設在玻璃基板的一面上的包含ITO膜的透明導電膜上，於80℃的熱板上進行1分鐘的加熱。其次，在230℃的熱板上進行30分鐘的加熱，由此而形成膜厚約80 nm的塗膜。使用具有輥(所述輥捲繞有棉制的布)的摩擦機，於輥的轉速為600 rpm、平臺的移動速度為2 cm/sec、毛壓入長度為0.4 mm的條件下對 該塗膜進行摩擦處理，賦予塗膜液晶配向能力而製成液晶配向膜。將具有該液晶配向膜的基板在超純水中進行1分鐘的超聲波清洗，然後於100℃的潔淨烘箱中進行10分鐘的乾燥。通過反復進行該些一系列操作而製造2枚(1對)具有液晶配向膜的基板。The liquid crystal alignment agent B for element production prepared in the above-described Example 15 was applied onto a transparent conductive film containing an ITO film on one surface of a glass substrate having a thickness of 1 mm, and was dried on a hot plate at 80 ° C using a rotator. 1 minute of heating. Next, heating was performed on a hot plate at 230 ° C for 30 minutes to form a coating film having a film thickness of about 80 nm. Using a friction machine having a roller (the cloth wrapped with a cotton cloth), the rotation speed of the roller was 600 rpm, the moving speed of the platform was 2 cm/sec, and the length of the hair pressing was 0.4 mm. The coating film was subjected to a rubbing treatment to impart a liquid crystal alignment ability to the coating film to form a liquid crystal alignment film. The substrate having the liquid crystal alignment film was subjected to ultrasonic cleaning in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C for 10 minutes. Two (one pair) of substrates having a liquid crystal alignment film were produced by repeating these series of operations.

其次，對於具有液晶配向膜的一對基板，於具有液晶配向膜的面的各個外緣塗布放入有直徑為3.5 μm的氧化鋁球的環氧數值接著劑後，以各個液晶配向膜面相對的方式使其重疊而進行壓接，使接著劑硬化。其次，自液晶注入口而於一對基板間填充向列型液晶(默克公司製造、MLC-6221)後，用丙烯酸類光硬化接著劑密封液晶注入口，於基板的外側的兩個面貼合偏光板，由此而製造水平配向型液晶顯示元件。Next, for a pair of substrates having a liquid crystal alignment film, an epoxy value-based adhesive having an alumina ball having a diameter of 3.5 μm is applied to each of the outer edges of the surface having the liquid crystal alignment film, and then the respective liquid crystal alignment film faces are opposed to each other. The way it is overlapped and crimped to harden the adhesive. Next, a nematic liquid crystal (manufactured by Merck & Co., Ltd., MLC-6221) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive, and the two sides of the substrate were attached. The polarizing plate is combined to produce a horizontal alignment type liquid crystal display element.

[製造例16~製造例26、比較製造例7~比較製造例9][Production Example 16 to Production Example 26, Comparative Production Example 7 to Comparative Production Example 9]

將所使用的液晶配向劑變更為實例16~實例26或比較例7~比較例9的元件製造用液晶配向劑B，除此以外利用與上述製造例15同樣的方法而製造水平配向型液晶顯示元件。The liquid crystal alignment agent to be used was changed to the liquid crystal alignment agent B for element production of Example 16 to Example 26 or Comparative Example 7 to Comparative Example 9, and a horizontal alignment type liquid crystal display was produced by the same method as the above Production Example 15. element.

<液晶配向膜的評價><Evaluation of liquid crystal alignment film> (1)印刷性的評價(1) Evaluation of printability

對於上述所調製的印刷性評價用液晶配向劑A，使用液晶配向膜印刷機(日本寫真印刷機株式會社製造、Angstromer、型號“S40L-532”)，於液晶配向劑於網紋輥 (anilox roll)上的滴加量為往返20滴(約0.2 g)的條件下，塗布於附有包含ITO膜的透明電極的玻璃基板的透明電極面上。另外，於同種型號的印刷機中所通常採用的滴加量為往返30滴(約0.3 g)，此處設為較通常情況下更嚴格的印刷條件。For the liquid crystal alignment agent A for the printability evaluation prepared above, a liquid crystal alignment film printer (manufactured by Nippon Photo Printing Co., Ltd., Angstromer, model "S40L-532") was used, and the liquid crystal alignment agent was applied to the anilox roller. The amount of dropwise addition on the (anilox roll) was applied to the transparent electrode surface of the glass substrate with the transparent electrode containing the ITO film under the condition of 20 drops (about 0.2 g). In addition, the amount of drop generally used in the same type of printing press is 30 drops (about 0.3 g), which is set to be more stringent than usual.

將塗布液晶配向劑後的基板於80℃的熱板上進行1分鐘的加熱(預焙)後，於180℃的熱板上進行10分鐘的加熱(後烘)，形成膜厚為80 nm的塗膜。用倍率為20倍的顯微鏡對該塗膜進行觀察，調查液晶配向劑的弹斥及塗布不均的有無。以如下方式進行評價：將並無彈斥及塗布不均的情況評價為印刷性“優良”，將稍許觀察到彈斥或塗布不均的情況評價為印刷性“良好”，將明確地觀察到彈斥或塗布不均的情況評價為印刷性“不良”。將其結果示於表3及表4中。The substrate coated with the liquid crystal alignment agent was heated (prebaked) on a hot plate at 80 ° C for 1 minute, and then heated on a hot plate at 180 ° C for 10 minutes (post-baking) to form a film thickness of 80 nm. Coating film. The coating film was observed with a microscope having a magnification of 20 times, and the presence or absence of repulsion and uneven coating of the liquid crystal alignment agent was examined. Evaluation was carried out in the following manner: the case where no repulsion and coating unevenness were evaluated as "excellent" in printability, and the case where repulsion or uneven coating was slightly observed was evaluated as "good" in printability, and it was clearly observed. The case of repulsion or uneven coating was evaluated as "bad" in printability. The results are shown in Tables 3 and 4.

(2)再加工性的評價(2) Evaluation of reworkability

用旋轉器將上述所調製的元件製造用液晶配向劑B塗布於厚度為1 mm的設於玻璃基板的一個面上的包含ITO膜的透明導電膜上，於熱板上、100℃下進行90秒的預焙，形成膜厚約80 nm的塗膜。反復進行該操作，製作4枚附有塗膜的基板。其次，於氮氣環境下、25℃的暗室中保管所得的基板，分別於12小時後、24小時後、48小時後、72小時後取出，於40℃的放入有NMP的燒杯中浸漬2分鐘。2分鐘後，將基板自燒杯中取出，用超純水進行數次清洗後，通過鼓風將表面的水滴除去，對基板進行 觀察，用光學顯微鏡觀察塗膜的殘存狀態。以如下方式進行評價：將即使保管時間為72小時的基板亦未殘存塗膜的情況評價為再加工性“優良”，將若為保管時間為48小時的基板則可剝離的情況評價為再加工性“良好”，將若為保管時間為24小時的基板則可剝離的情況評價為再加工性“稍好”，將若為保管時間為12小時的基板則可剝離的情況評價為再加工性“尚可”，將即使保管時間為12小時的基板亦無法剝離塗膜的情況評價為再加工性“不良”。將評價結果示於表3及表4中。The liquid crystal alignment agent B for element preparation prepared above was applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm by a spinner, and dried on a hot plate at 100 ° C. Pre-baked in seconds to form a coating film having a film thickness of about 80 nm. This operation was repeated to produce four substrates with a coating film. Next, the obtained substrate was stored in a dark room at 25 ° C in a nitrogen atmosphere, and taken out after 12 hours, 24 hours, 48 hours, and 72 hours, and immersed in a beaker containing NMP at 40 ° C for 2 minutes. . After 2 minutes, the substrate was taken out from the beaker, washed several times with ultrapure water, and the water droplets on the surface were removed by air blowing to perform substrate polishing. Observation was carried out, and the residual state of the coating film was observed with an optical microscope. The evaluation was carried out in the following manner: the case where the coating film remained in the substrate having a storage time of 72 hours was evaluated as "excellent", and the case where the substrate was stored for 48 hours was evaluated as reprocessing. When the substrate having a storage time of 24 hours is peelable, the reworkability is "slightly better", and the case where the substrate is stored for 12 hours is evaluated as reworkability. "It is acceptable", and the case where the coating film cannot be peeled off even if the substrate has a storage time of 12 hours is evaluated as "defective" in reworkability. The evaluation results are shown in Tables 3 and 4.

<液晶顯示元件的評價><Evaluation of Liquid Crystal Display Element> (1)初始電壓保持率的評價(1) Evaluation of initial voltage holding ratio

對於製造不久後的液晶顯示元件，於60℃的溫度下，以60微秒的施加時間、167毫秒的間隔施加5 V的電壓後，測定自解除施加起167毫秒後的電壓保持率(初始電壓保持率)。測定裝置使用東陽技術株式會社(Toyo Corporation)製造的品名“VHR-1”。將其結果示於下述表3及表4中。For a liquid crystal display element which was manufactured shortly after, a voltage of 5 V was applied at an application time of 60 μsec and an interval of 167 msec at a temperature of 60 ° C, and then the voltage holding ratio (initial voltage) after 167 msec from the release of the application was measured. Retention rate). The measurement device used the product name "VHR-1" manufactured by Toyo Corporation. The results are shown in Tables 3 and 4 below.

(2)耐光性的評價(2) Evaluation of light resistance

對測定初始電壓保持率VH₁ 後的液晶顯示元件的其中一方，使用以碳弧為光源的耐候試驗機而進行1000小時的光照射。對於光照射後的液晶單元，利用與上述同樣的方法而測定電壓保持率。將該值作為光照射後的電壓保持率VH₂ 、將初始電壓保持率設為VH₁ 時，將VH₁ 減去VH₂ 而求出的電壓保持率的減少量作為△VHR，利用△VHR而 評價耐光性。將測定結果示於下述的表3及表4中。 _One of the liquid crystal display elements after the initial voltage holding ratio VH ₁ was measured and subjected to light irradiation for 1,000 hours using a weather resistance tester using a carbon arc as a light source. The voltage holding ratio was measured by the same method as described above for the liquid crystal cell after light irradiation. When the value is the voltage holding ratio VH ₂ after the light irradiation and the initial voltage holding ratio is VH ₁ , the amount of decrease in the voltage holding ratio obtained by subtracting VH ₂ from VH _{1 is} ΔVHR, and ΔVHR is used. Evaluation of light resistance. The measurement results are shown in Tables 3 and 4 below.

(3)耐高溫高濕性的評價(3) Evaluation of high temperature and high humidity resistance

將測定初始電壓保持率VH₁ 後的液晶顯示元件的另一方於設定為60℃、濕度90%的烘箱中進行300小時的保管後，利用與上述同樣的方法而測定電壓保持率。將該值作為賦予應力後的電壓保持率VH₄ 、將初始電壓保持率設為VH₃ 時，將VH₃ 減去VH₄ 而求出的電壓保持率的減少量作為△VHR'，利用△VHR'而評價耐高溫高濕性。將測定結果示於下述的表3及表4中。The other of the liquid crystal display elements after the measurement of the initial voltage holding ratio VH ₁ was stored in an oven set to 60° C. and a humidity of 90% for 300 hours, and then the voltage holding ratio was measured by the same method as described above. When the value is the voltage holding ratio VH ₄ after the stress is applied and the initial voltage holding ratio is VH ₃ , the amount of decrease in the voltage holding ratio obtained by subtracting VH ₄ from VH _{3 is} ΔVHR′, and ΔVHR is used. 'And evaluate the high temperature and high humidity. The measurement results are shown in Tables 3 and 4 below.

於表3及表4中，添加劑的數值表示相對於液晶配向劑中所含有的聚合物100重量份的含有比例[重量份]。而且，添加劑的略稱分別是以下的含義。In Tables 3 and 4, the numerical value of the additive indicates the content ratio [parts by weight] based on 100 parts by weight of the polymer contained in the liquid crystal alignment agent. Moreover, the abbreviations of the additives are respectively the following meanings.

M：N,N,N',N'-四縮水甘油基-間苯二甲胺M:N,N,N',N'-tetraglycidyl-m-xylylenediamine

N：TINUVIN622(胺類抗氧化劑)N:TINUVIN622 (amine antioxidant)

O：化合物(EPS-1)O: Compound (EPS-1)

P：二季戊四醇六丙烯酸酯P: dipentaerythritol hexaacrylate

Q：N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷Q: N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

如表3及表4所示，於使用實例的液晶配向劑而製造的液晶顯示元件中，於聚醯亞胺類及聚醯胺酸類的任意者 中均是暴露在光照射或高溫高濕的環境下的情況下的電壓保持率的降低量少，且耐光性及耐高溫高濕性優異。而且，關於對於基板的剝離性(再加工性)或印刷性，亦均良好。As shown in Tables 3 and 4, in the liquid crystal display element produced by using the liquid crystal alignment agent of the example, any of polyimine and polyglycolic acid is used. In the case where the light is exposed to light or high temperature and high humidity, the amount of decrease in the voltage holding ratio is small, and the light resistance and the high temperature and high humidity are excellent. Further, the peeling property (reworkability) or the printability with respect to the substrate were also good.

相對於此，於比較例中，若聚醯亞胺類、聚醯胺酸類的各個與實例相比較，則△VHR及△VHR'的至少任意者均大於實例的△VHR及△VHR'的至少任意者，耐光性或耐高溫高濕性差。On the other hand, in the comparative example, if each of the polyimine and the polyamine is compared with the example, at least any of ΔVHR and ΔVHR' is greater than at least ΔVHR and ΔVHR' of the example. Any one, poor light resistance or high temperature and high humidity.

Claims (9)

一種液晶配向劑，其含有選自由使四羧酸二酐與二胺反應所得的聚醯胺酸及使該聚醯胺酸進行脫水閉環而成的聚醯亞胺所構成的群組中的至少一種聚合物，其特徵在於：所述二胺包含下述式(A)所表示的化合物(a)， 式(A)中，Am¹ 是與氮原子一同形成吡咯烷環、哌啶環或六亞甲基亞胺環的2價基，該些基的環部分上亦可鍵結取代基；其中，於Am¹ 中，構成環的氮原子鍵結於X² 上；X¹ 是單鍵、氧原子、羰基、*-COO-、*-OCO-、-NH-、*-Ar¹ -O-、*-O-Ar¹ -、*-COO-Ar¹ -、或*-R³ -OCO-，其中，Ar¹ 是伸苯基或於伸苯基上鍵結有取代基的2價基，R³ 是碳數為1或2的烷二基；“*”表示與含氮雜環的鍵結的鍵；X² 是單鍵或羰基；R¹ 是碳數為1~10的烷基、碳數為3~12的脂環族烴基、碳數為6~12的芳香族烴基、羥基、鹵素原子、硝基或氰基，其中上述烴基的碳-碳鍵間可具有-O-、-CO-、-COO-或-OCO-，上述烴基所具有的氫原子的至少一部分可被鹵素原子取代；r分別獨立為0~4的整 數；其中，於r的合計為2以上的情況下，多個R¹ 獨立地具有上述定義。A liquid crystal alignment agent containing at least one selected from the group consisting of polylysine obtained by reacting tetracarboxylic dianhydride with a diamine and polyamidene obtained by dehydrating and ring-closing the polyamic acid A polymer characterized in that the diamine comprises the compound (a) represented by the following formula (A), In the formula (A), Am ¹ is a divalent group which forms a pyrrolidine ring, a piperidine ring or a hexamethyleneimine ring together with a nitrogen atom, and the ring moiety of the group may also bond a substituent; In Am ¹ , the nitrogen atom constituting the ring is bonded to X ² ; X ¹ is a single bond, an oxygen atom, a carbonyl group, *-COO-, *-OCO-, -NH-, *-Ar ¹ -O-, *-O-Ar ¹ -, *-COO-Ar ¹ -, or *-R ³ -OCO-, wherein Ar ¹ is a diphenyl group or a divalent group having a substituent bonded to a phenyl group, R ³ is an alkanediyl group having a carbon number of 1 or 2; "*" represents a bond bonded to a nitrogen-containing heterocyclic ring; X ² is a single bond or a carbonyl group; and R ¹ is an alkyl group having 1 to 10 carbon atoms, carbon The alicyclic hydrocarbon group of 3 to 12, the aromatic hydrocarbon group having 6 to 12 carbon atoms, a hydroxyl group, a halogen atom, a nitro group or a cyano group, wherein the hydrocarbon group may have -O-, -CO between carbon-carbon bonds -, -COO- or -OCO-, at least a part of the hydrogen atoms of the hydrocarbon group may be substituted by a halogen atom; r is independently an integer of 0 to 4; wherein, when the total of r is 2 or more, R ¹ independently has the above definition. 如申請專利範圍第1項所述的液晶配向劑，其中，所述化合物(a)以下述式(A-1)所表示， 式(A-1)中，X¹ 是單鍵、氧原子、羰基、*-COO-、*-OCO-、-NH-、*-Ar¹ -O-、*-O-Ar¹ -、*-COO-Ar¹ -、或*-R³ -OCO-，其中，Ar¹ 是伸苯基或於伸苯基上鍵結有取代基的2價基，R³ 是碳數為1或2的烷二基；“*”表示與含氮雜環的鍵結的鍵；X² 是單鍵或羰基；R¹ 及R⁴ 分別獨立為碳數為1~10的烷基、碳數為3~12的脂環族烴基、碳數為6~12的芳香族烴基、羥基、鹵素原子、硝基或氰基，其中上述烴基的碳-碳鍵間可具有-O-、-CO-、-COO-或-OCO-，上述烴基所具有的氫原子的至少一部分可被鹵素原子取代；r及s分別獨立為0~4的整數；其中，於r的合計為2以上的情況下，多個R¹ 獨立地具有上述定義，於s為2以上的情況下，多個R⁴ 獨立地具有上述定義。The liquid crystal alignment agent according to claim 1, wherein the compound (a) is represented by the following formula (A-1). In the formula (A-1), X ¹ is a single bond, an oxygen atom, a carbonyl group, *-COO-, *-OCO-, -NH-, *-Ar ¹ -O-, *-O-Ar ¹ -, * -COO-Ar ¹ -, or *-R ³ -OCO-, wherein Ar ¹ is a phenyl group or a divalent group having a substituent bonded to a phenyl group, and R ³ is a carbon number of 1 or 2. An alkanediyl group; "*" represents a bond to a nitrogen-containing heterocyclic ring; X ² is a single bond or a carbonyl group; and R ¹ and R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms and a carbon number of 3 to 3; An alicyclic hydrocarbon group of 12, an aromatic hydrocarbon group having 6 to 12 carbon atoms, a hydroxyl group, a halogen atom, a nitro group or a cyano group, wherein the hydrocarbon group may have -O-, -CO-, -COO between carbon-carbon bonds -O-OCO-, at least a part of the hydrogen atoms of the hydrocarbon group may be substituted by a halogen atom; and r and s are each independently an integer of 0 to 4; wherein, when the total of r is 2 or more, a plurality of R ¹ independently has the above definition, and when s is 2 or more, a plurality of R ⁴ independently have the above definition. 如申請專利範圍第1項或第2項所述的液晶配向 劑，其中，所述X² 是單鍵。The liquid crystal alignment agent according to claim 1 or 2, wherein the X ² is a single bond. 如申請專利範圍第1項或第2項所述的液晶配向劑，其中，所述X¹ 是*-COO-、*-OCO-、-NH-或*-R³ -OCO-，其中，R³ 是碳數為1或2的烷二基；“*”表示與含氮雜環的鍵結的鍵。The liquid crystal alignment agent according to claim 1 or 2, wherein the X ¹ is *-COO-, *-OCO-, -NH- or *-R ³ -OCO-, wherein R ³ is an alkanediyl group having a carbon number of 1 or 2; "*" represents a bond to a nitrogen-containing heterocyclic ring. 如申請專利範圍第1項或第2項所述的液晶配向劑，其中，所述四羧酸二酐包含選自由2,3,5-三羧基環戊基乙酸二酐及1,2,3,4-環丁烷四羧酸二酐所構成的群組的至少一種。 The liquid crystal alignment agent according to claim 1 or 2, wherein the tetracarboxylic dianhydride comprises a solvent selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,2,3 At least one of the group consisting of 4-cyclobutanetetracarboxylic dianhydride. 一種液晶配向膜，其是使用如申請專利範圍第1項至第5項中任一項所述的液晶配向劑而形成的液晶配向膜。 A liquid crystal alignment film which is a liquid crystal alignment film formed by using the liquid crystal alignment agent according to any one of claims 1 to 5. 一種液晶顯示元件，包括如申請專利範圍第6項所述的液晶配向膜。 A liquid crystal display element comprising the liquid crystal alignment film according to item 6 of the patent application. 一種聚合物，其是使包含下述式(A)所表示的化合物(a)的二胺與四羧酸二酐反應所得的聚合物， 式(A)中，Am¹ 是與氮原子一同形成吡咯烷環、哌啶環或六亞甲基亞胺環的2價基，該些基的環部分上亦可 鍵結取代基；其中，於Am¹ 中，構成環的氮原子鍵結於X² 上；X¹ 是單鍵、氧原子、羰基、*-COO-、*-OCO-、-NH-、*-Ar¹ -O-、*-O-Ar¹ -、*-COO-Ar¹ -、或*-R³ -OCO-，其中，Ar¹ 是伸苯基或於伸苯基上鍵結有取代基的2價基，R³ 是碳數為1或2的烷二基；“*”表示與含氮雜環的鍵結的鍵；X² 是單鍵或羰基；R¹ 是碳數為1~10的烷基、碳數為3~12的脂環族烴基、碳數為6~12的芳香族烴基、羥基、鹵素原子、硝基或氰基，其中上述烴基的碳-碳鍵間可具有-O-、-CO-、-COO-或-OCO-，上述烴基所具有的氫原子的至少一部分可被鹵素原子取代；r分別獨立為0~4的整數；其中，於r的合計為2以上的情況下，多個R¹ 獨立地具有上述定義。a polymer obtained by reacting a diamine containing a compound (a) represented by the following formula (A) with a tetracarboxylic dianhydride, In the formula (A), Am ¹ is a divalent group which forms a pyrrolidine ring, a piperidine ring or a hexamethyleneimine ring together with a nitrogen atom, and the ring moiety of the group may also bond a substituent; In Am ¹ , the nitrogen atom constituting the ring is bonded to X ² ; X ¹ is a single bond, an oxygen atom, a carbonyl group, *-COO-, *-OCO-, -NH-, *-Ar ¹ -O-, *-O-Ar ¹ -, *-COO-Ar ¹ -, or *-R ³ -OCO-, wherein Ar ¹ is a diphenyl group or a divalent group having a substituent bonded to a phenyl group, R ³ is an alkanediyl group having a carbon number of 1 or 2; "*" represents a bond bonded to a nitrogen-containing heterocyclic ring; X ² is a single bond or a carbonyl group; and R ¹ is an alkyl group having 1 to 10 carbon atoms, carbon The alicyclic hydrocarbon group of 3 to 12, the aromatic hydrocarbon group having 6 to 12 carbon atoms, a hydroxyl group, a halogen atom, a nitro group or a cyano group, wherein the hydrocarbon group may have -O-, -CO between carbon-carbon bonds -, -COO- or -OCO-, at least a part of the hydrogen atoms of the hydrocarbon group may be substituted by a halogen atom; r is independently an integer of 0 to 4; wherein, when the total of r is 2 or more, R ¹ independently has the above definition. 一種化合物，其以下述式(A)所表示， 式(A)中，Am¹ 是與氮原子一同形成吡咯烷環、哌啶環或六亞甲基亞胺環的2價基，該些基的環部分上亦可鍵結取代基；其中，於Am¹ 中，構成環的氮原子鍵結於X² 上；X¹ 是單鍵、氧原子、羰基、*-COO-、*-OCO-、-NH-、*-Ar¹ -O-、*-O-Ar¹ -、*-COO-Ar¹ -、或*-R³ -OCO-，其中，Ar¹ 是伸苯基或於伸苯基上鍵結有取代基的2價基，R³ 是 碳數為1或2的烷二基；“*”表示與含氮雜環的鍵結的鍵；X² 是單鍵或羰基；R¹ 是碳數為1~10的烷基、碳數為3~12的脂環族烴基、碳數為6~12的芳香族烴基、羥基、鹵素原子、硝基或氰基，其中上述烴基的碳-碳鍵間可具有-O-、-CO-、-COO-或-OCO-，上述烴基所具有的氫原子的至少一部分可被鹵素原子取代；r分別獨立為0~4的整數；其中，於r的合計為2以上的情況下，多個R¹ 獨立地具有上述定義。a compound represented by the following formula (A), In the formula (A), Am ¹ is a divalent group which forms a pyrrolidine ring, a piperidine ring or a hexamethyleneimine ring together with a nitrogen atom, and the ring moiety of the group may also bond a substituent; In Am ¹ , the nitrogen atom constituting the ring is bonded to X ² ; X ¹ is a single bond, an oxygen atom, a carbonyl group, *-COO-, *-OCO-, -NH-, *-Ar ¹ -O-, *-O-Ar ¹ -, *-COO-Ar ¹ -, or *-R ³ -OCO-, wherein Ar ¹ is a diphenyl group or a divalent group having a substituent bonded to a phenyl group, R ³ is an alkanediyl group having a carbon number of 1 or 2; "*" represents a bond bonded to a nitrogen-containing heterocyclic ring; X ² is a single bond or a carbonyl group; and R ¹ is an alkyl group having 1 to 10 carbon atoms, carbon The alicyclic hydrocarbon group of 3 to 12, the aromatic hydrocarbon group having 6 to 12 carbon atoms, a hydroxyl group, a halogen atom, a nitro group or a cyano group, wherein the hydrocarbon group may have -O-, -CO between carbon-carbon bonds -, -COO- or -OCO-, at least a part of the hydrogen atoms of the hydrocarbon group may be substituted by a halogen atom; r is independently an integer of 0 to 4; wherein, when the total of r is 2 or more, R ¹ independently has the above definition.