TWI632197B

TWI632197B - Liquid crystal alignment agent, liquid crystal alignment film, method for producing liquid crystal alignment film, liquid crystal display element and method for producing liquid crystal display element

Info

Publication number: TWI632197B
Application number: TW103138282A
Authority: TW
Inventors: 秋池利之; 的場拓巳
Original assignee: Jsr股份有限公司
Priority date: 2013-11-11
Filing date: 2014-11-05
Publication date: 2018-08-11
Also published as: JP2015094830A; CN104629774B; CN104629774A; KR20150054652A; JP6349685B2; TW201518411A; KR102157727B1

Abstract

本發明提供一種液晶配向劑，其可獲得液晶配向性及配向穩定性良好的液晶配向膜。本發明的液晶配向劑中含有聚合物成分、及下述式(1)所表示的化合物(D)。 The invention provides a liquid crystal alignment agent, which can obtain a liquid crystal alignment film with good liquid crystal alignment and alignment stability. The liquid crystal alignment agent of this invention contains a polymer component and the compound (D) represented by following formula (1).

(式中，A¹為包含聚合性不飽和鍵的基團，A²為可與環氧基進行反應的官能基，R¹為(m+n)價有機基；m為2~18的整數，n為1~18的整數；其中，滿足(m+n)≦20。) (In the formula, A ¹ is a group containing a polymerizable unsaturated bond, A ² is a functional group capable of reacting with an epoxy group, R ¹ is a (m + n) -valent organic group, and m is an integer from 2 to 18. , N is an integer from 1 to 18, where (m + n) ≦ 20 is satisfied.)

Description

液晶配向劑、液晶配向膜、液晶配向膜的製造方法、液晶顯示元件以及液晶顯示元件的製造方法 Liquid crystal alignment agent, liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal display element, and method for manufacturing liquid crystal display element

本發明是有關於一種液晶配向劑、液晶配向膜、液晶配向膜的製造方法、液晶顯示元件以及液晶顯示元件的製造方法。 The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a method for manufacturing a liquid crystal alignment film, a liquid crystal display element, and a method for manufacturing a liquid crystal display element.

以往，液晶顯示元件已開發出電極結構或所使用的液晶分子的物性等不同的多種驅動方式，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、多域垂直配向(Multidomain Vertical Alignment，MVA)型、共面切換(In-Plane Switching，IPS)型、邊緣場切換(Fringe Field Switching，FFS)型等各種液晶顯示元件。這些液晶顯示元件具有用以使液晶分子進行配向的液晶配向膜。就耐熱性、機械強度、與液晶的親和性等各種特性良好的方面而言，液晶配向膜的材料通常使用聚醯胺酸或聚醯亞胺。另外，還提出使用將可表現出所需功能的基團導入至側鏈中的聚有機矽氧烷來作為液晶配向劑的聚合物成分(例如參照專利文獻1)。該專利文獻1中公開了：使包含具有鏈狀烷基的矽烷化合物的水解性矽烷化合物在乙二酸以及醇的存在下進行反應，使用通過該反應而獲得的聚有機矽氧烷作為液晶配向劑的聚合物成分。 In the past, liquid crystal display devices have developed various driving methods such as electrode structures or physical properties of liquid crystal molecules used. For example, Twisted Nematic (TN) or Super-Twisted Nematic are known. , STN) type, Vertical Alignment (VA) type, Multidomain Vertical Alignment (MVA) type, In-Plane Switching (IPS) type, Fringe Field Switching (FFS) ) Type and other liquid crystal display elements. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. In terms of various properties such as heat resistance, mechanical strength, and affinity with liquid crystals, polyamines are generally used as the material of the liquid crystal alignment film. Acid or polyimide. It is also proposed to use a polyorganosiloxane in which a group capable of exhibiting a desired function is introduced into a side chain as a polymer component of a liquid crystal alignment agent (for example, refer to Patent Document 1). Patent Document 1 discloses that a hydrolyzable silane compound containing a silane compound having a chain alkyl group is reacted in the presence of oxalic acid and an alcohol, and a polyorganosiloxane obtained by the reaction is used as a liquid crystal alignment. Polymer composition of the agent.

另外，近年來，作為用以表現出預傾角特性的新技術，提出了聚合物穩定配向(Polymer Sustained Alignment，PSA)技術。PSA技術為如下技術：構築將光聚合性化合物混入液晶層中而成的液晶單元，構築液晶單元後，對液晶層施加電壓，在使液晶分子傾斜配向的狀態下進行光照射，由此光聚合性化合物進行聚合而控制液晶的分子配向(例如參照專利文獻2)。依據該PSA技術，具有可實現視角的擴大或高速回應化的優點。 In addition, in recent years, as a new technology for expressing a pretilt angle characteristic, A Polymer Sustained Alignment (PSA) technology was proposed. The PSA technology is a technology of constructing a liquid crystal cell in which a photopolymerizable compound is mixed into a liquid crystal layer. After the liquid crystal cell is constructed, a voltage is applied to the liquid crystal layer and light is irradiated in a state where the liquid crystal molecules are tilted and aligned, thereby photopolymerizing The molecular alignment of the liquid crystal is controlled by polymerizing the sexual compound (for example, refer to Patent Document 2). According to this PSA technology, there is an advantage that the viewing angle can be enlarged or a high-speed response can be realized.

另外，本申請人提出了如下技術：使用一種液晶配向劑(該液晶配向劑包含具有(甲基)丙烯醯基的聚有機矽氧烷)，在一對基板上形成塗膜，並且構築具備該一對基板的液晶單元，然後，在對一對基板中的導電膜間施加電壓的狀態下，對液晶單元進行光照射(例如參照專利文獻3)。 In addition, the present applicant has proposed a technique for forming a coating film on a pair of substrates using a liquid crystal alignment agent (the liquid crystal alignment agent includes a polyorganosiloxane having a (meth) acrylfluorenyl group), and constructing The liquid crystal cells of the pair of substrates are then irradiated with light while a voltage is applied between the conductive films in the pair of substrates (for example, refer to Patent Document 3).

作為使用液晶配向劑來對所形成的高分子薄膜賦予液晶配向能力的方法，近年來，提出了利用光異構化或光二聚化、光分解等的光配向法來代替摩擦法的技術。該光配向法為如下方法：通過對形成於基板上的感放射線性有機薄膜，照射偏光或者非偏光的放射線來對膜賦予各向異性，由此控制液晶分子的配向。依據該方法，與現有的摩擦法相比，可抑制步驟內的灰塵或靜電的產生，因此可抑制因灰塵等而引起的顯示不良的產生或良率的下降。另外，還具有可對形成於基板上的塗膜均勻地賦予液晶配向能力的優點。 As a method of using a liquid crystal alignment agent to impart liquid crystal alignment ability to a formed polymer film, in recent years, a technology using a photo-alignment method such as photo isomerization, photo-dimerization, and photo-decomposition instead of the rubbing method has been proposed. The photo-alignment method is a method of irradiating polarizing light onto a radiation-sensitive organic thin film formed on a substrate or Unpolarized radiation imparts anisotropy to the film, thereby controlling the alignment of liquid crystal molecules. According to this method, as compared with the conventional rubbing method, generation of dust or static electricity in the step can be suppressed, so it is possible to suppress generation of display failure or decrease in yield due to dust or the like. In addition, there is an advantage that a liquid crystal alignment ability can be uniformly imparted to a coating film formed on a substrate.

[現有技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平9-281502號公報 [Patent Document 1] Japanese Patent Laid-Open No. 9-281502

[專利文獻2]日本專利特開2003-149647號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2003-149647

[專利文獻3]日本專利特開2011-118358號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2011-118358

在通過紫外線等的照射而產生化學變化的光配向法的情況下，存在與利用現有的摩擦處理的液晶配向膜相比較，在液晶的配向限制力的方面差的傾向。考慮到所述方面，在使用光配向法的情況下，有時出於提高液晶的配向限制力的目的而進行PSA處理。然而，即便進行PSA處理，也無法充分提高液晶分子的配向限制力，特別是在橫向電場方式的液晶顯示元件中會產生顯示品質下降、或在長時間的連續驅動後產生殘像的問題。另外，在垂直配向型液晶顯示元件的製作中，有時也對所構築的液晶單元進行光照射處理來提高液晶的配向限制力。然而，在進行所述處理的情況下，存在容易產生因長時間的連續驅動而引起的電壓保持率的下降，可靠性差的傾向。 In the case of a photo-alignment method in which a chemical change is caused by irradiation with ultraviolet rays or the like, there is a tendency that a liquid crystal alignment film using a conventional rubbing treatment is inferior in alignment regulating force. In view of the above, when the photo-alignment method is used, the PSA treatment may be performed for the purpose of increasing the alignment restricting force of the liquid crystal. However, even if PSA treatment is performed, the alignment restraining force of liquid crystal molecules cannot be sufficiently improved. In particular, in a liquid crystal display element of a lateral electric field method, problems such as a reduction in display quality or an afterimage may occur after continuous driving for a long time. In addition, in the production of a vertical alignment type liquid crystal display element, a light irradiation treatment may be performed on the constructed liquid crystal cell to increase the alignment control force of the liquid crystal. However, in the case where the processing is performed, there is a possibility that a voltage due to continuous driving for a long period of time is easily generated. The retention rate decreases, and the reliability tends to be poor.

本發明是鑒於所述課題而形成，主要目的在於提供一種可獲得液晶配向性及配向穩定性良好的液晶配向膜的液晶配向劑。另外，另一目的在於提供一種電壓保持率或殘像特性等各種特性良好的液晶顯示元件。 The present invention has been made in view of the problems described above, and a main object thereof is to provide A liquid crystal alignment agent for a liquid crystal alignment film with good liquid crystal alignment and alignment stability can be obtained. Another object is to provide a liquid crystal display element having various characteristics such as a voltage retention ratio and an afterimage characteristic.

本發明者等人為了達成如上所述的現有技術的課題而進行了努力研究，結果發現，通過使液晶配向劑中含有特定的化合物，可解決所述課題，從而完成了本發明。具體而言，通過本發明來提供以下的液晶配向劑、液晶配向膜、液晶配向膜的製造方法、液晶顯示元件以及液晶顯示元件的製造方法。 The present inventors have made intensive studies in order to achieve the problems of the related art described above, and as a result, they have found that the problems can be solved by including a specific compound in the liquid crystal alignment agent, and the present invention has been completed. Specifically, the present invention provides the following liquid crystal alignment agent, liquid crystal alignment film, method for producing liquid crystal alignment film, liquid crystal display element, and method for producing liquid crystal display element.

本發明的一方面為提供一種液晶配向劑，其含有聚合物成分、及下述式(1)所表示的化合物(D)。 One aspect of the present invention is to provide a liquid crystal alignment agent comprising a polymer component and a compound (D) represented by the following formula (1).

(式(1)中，A¹為包含聚合性不飽和鍵的基團，A²為可與環氧基進行反應的官能基，R¹為(m+n)價有機基；m為2~18的整數，n為1~18的整數；其中，滿足(m+n)≦20。) (In formula (1), A ¹ is a group containing a polymerizable unsaturated bond, A ² is a functional group capable of reacting with an epoxy group, R ¹ is a (m + n) -valent organic group, and m is 2 to An integer of 18, and n is an integer of 1 to 18, where (m + n) ≦ 20 is satisfied.)

本發明的一方面為提供一種液晶配向膜的製造方法，其包括：將所述液晶配向劑塗布於基板上而形成塗膜的步驟、以及對該塗膜進行光照射的步驟。另外，提供一種液晶顯示元件的製造方法，其包括：在一對基板的各表面上分別塗布所述液晶配向劑，繼而對其進行加熱而形成塗膜的步驟；以塗膜相對的方式，將形成有該塗膜的一對基板隔著液晶分子的層而對向配置，來構築液晶單元的步驟；以及自該液晶單元的外側進行光照射的步驟。 An aspect of the present invention is to provide a method for manufacturing a liquid crystal alignment film, comprising: a step of applying the liquid crystal alignment agent on a substrate to form a coating film; and a step of irradiating the coating film with light. In addition, a method for manufacturing a liquid crystal display element is provided. A manufacturing method includes the steps of: coating the liquid crystal alignment agent on each surface of a pair of substrates, and then heating the liquid crystal alignment agent to form a coating film; and forming the coating film on the pair with the coating films facing each other. A step of arranging substrates facing each other with a layer of liquid crystal molecules therebetween to construct a liquid crystal cell; and a step of irradiating light from the outside of the liquid crystal cell.

利用本發明的液晶配向劑，可獲得液晶配向性及配向穩定性良好的液晶配向膜。另外，具備使用該液晶配向劑來製作的液晶配向膜的液晶顯示元件的電壓保持率或殘像特性等各種特性良好。 By using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film with good liquid crystal alignment and alignment stability can be obtained. In addition, various characteristics such as voltage retention and afterimage characteristics of a liquid crystal display element including a liquid crystal alignment film produced using the liquid crystal alignment agent are good.

11、12‧‧‧電極 11, 12‧‧‧ electrodes

A、B‧‧‧基板 A, B‧‧‧ substrate

圖1是表示經圖案化為梳齒狀的透明電極的圖案的圖。 FIG. 1 is a diagram showing a pattern of a transparent electrode patterned in a comb-tooth shape.

圖2是表示經圖案化為狹縫狀的透明電極的圖案的圖。 FIG. 2 is a diagram showing a pattern of a transparent electrode patterned into a slit shape.

本發明的液晶配向劑含有聚合物成分、與多官能性的特定化合物(D)。以下，對本發明的液晶配向劑中所含的各成分、以及視需要而任意調配的其他成分進行說明。 The liquid crystal alignment agent of the present invention contains a polymer component and a polyfunctional specific compound (D). Hereinafter, each component contained in the liquid crystal aligning agent of this invention, and other components arbitrarily mix | blended as needed are demonstrated.

聚合物成分 Polymer composition

本發明的聚合物成分並無特別限定，例如可列舉：聚醯胺酸、聚醯胺酸酯、聚醯亞胺、聚有機矽氧烷、聚(甲基)丙烯酸酯、聚酯、聚醯胺、纖維素衍生物、聚縮醛、聚苯乙烯衍生物、聚(苯乙烯-苯基順丁烯二醯亞胺)衍生物等。這些聚合物中，本發明的液晶配向劑優選為包含選自由聚醯胺酸、聚醯胺酸酯、聚醯亞胺及聚有機矽氧烷所組成的組群中的至少一種聚合物(以下也稱為「特定聚合物」)作為聚合物成分。 The polymer component of the present invention is not particularly limited, and examples thereof include polyamic acid, polyamidate, polyimide, polyorganosiloxane, poly (meth) acrylate, polyester, and polyfluorene. Amines, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) imine derivatives, and the like. Among these polymers, the liquid crystal compound of the present invention The agent is preferably composed of at least one polymer (hereinafter also referred to as "specific polymer") selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyorganosiloxane. As a polymer component.

<聚醯胺酸> <Polyamic acid>

本發明的聚醯胺酸例如可通過使四羧酸二酐與二胺進行反應來合成。 The polyamino acid of the present invention can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine.

[四羧酸二酐] [Tetracarboxylic dianhydride]

用於合成本發明的聚醯胺酸的四羧酸二酐例如可列舉脂肪族四羧酸二酐、脂環式四羧酸二酐、芳香族四羧酸二酐等。作為這些四羧酸二酐的具體例，脂肪族四羧酸二酐例如可列舉：1,2,3,4-丁烷四羧酸二酐等；脂環式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)-萘并[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)-萘并[1,2-c]呋喃-1,3-二酮、3-氧雜雙環[3.2.1]辛烷-2,4-二酮-6-螺環-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：均苯四甲酸二酐等；除此以外，還可使用日本專利特開2010-97188號公報中記載的四羧酸二酐等。此外，所述四羧酸二酐可單獨使用1種或者將2種以上組合使用。 Examples of the tetracarboxylic dianhydride used to synthesize the polyamic acid of the present invention include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. As specific examples of these tetracarboxylic dianhydrides, examples of the aliphatic tetracarboxylic dianhydride include 1, 2, 3, 4-butane tetracarboxylic dianhydride, and the like; and examples of the alicyclic tetracarboxylic dianhydride include : 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic 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-furyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [ 3.2.1] Octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3- Furyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-di Anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] Monoalkane-3,5,8,10-tetraketone, cyclohexanetetracarboxylic dianhydride, etc .; Examples of the aromatic tetracarboxylic dianhydride: pyromellitic dianhydride; etc. Tetracarboxylic dianhydride and the like described in Japanese Patent Laid-Open No. 2010-97188. The tetracarboxylic dianhydrides may be used alone or in combination of two or more.

[二胺] [Diamine]

用於合成本發明的聚醯胺酸的二胺例如可列舉：脂肪族二胺、脂環式二胺、芳香族二胺、二胺基有機矽氧烷等。作為這些二胺的具體例，脂肪族二胺例如可列舉：間苯二甲胺、1,3-丙二胺、四亞甲基二胺、五亞甲基二胺、六亞甲基二胺等；脂環式二胺例如可列舉：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：十二烷氧基二胺基苯、十四烷氧基二胺基苯、十五烷氧基二胺基苯、十六烷氧基二胺基苯、十八烷氧基二胺基苯、膽甾烷基氧基二胺基苯、膽甾烯基氧基二胺基苯、二胺基苯甲酸膽甾烷基酯、二胺基苯甲酸膽甾烯基酯、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、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、N-(2,4-二胺基苯基)-4-(4-庚基環己基)苯甲醯胺、下述式(a-1)所表示的化合物等含液晶配向性基的二胺：[化2] Examples of the diamine used to synthesize the polyamidic acid of the present invention include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamine organosiloxanes. As specific examples of these diamines, examples of the aliphatic diamine include m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), and 1,3-bis (aminomethyl) cyclohexyl. Examples of the aromatic diamine include dodecyloxydiaminobenzene, tetradecyloxydiaminobenzene, pentadecyloxydiaminobenzene, and cetyloxydiaminebenzene. Octadecyloxydiaminobenzene, cholesteryloxydiaminobenzene, cholestyloxydiaminobenzene, cholesteryl diaminobenzoate, choline diaminobenzoate Sterolyl ester, lanosteryl diaminobenzoate, 3,6-bis (4-aminobenzyloxy) cholestane, 3,6-bis (4-aminophenoxy) Cholesterol, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) Phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, N- (2,4-di Isotropic liquid crystal alignment containing a diamine group-yl) -4- (4-heptyl cyclohexyl) benzoyl amine compound represented by the following formula (a-1): [Chemical Formula 2]

(式(a-1)中，X^I及X^II分別獨立地為單鍵、-O-、-COO-或者-OCO-，R^I及R^II分別獨立地為碳數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，d為0或1；其中，a及b不會同時為0) (In formula (a-1), X ^I and X ^II are each independently a single bond, -O-, -COO-, or -OCO-, and R ^I and R ^II are each independently alkane having 1 to 3 carbon atoms. Base, a is 0 or 1, b is an integer from 0 to 2, c is an integer from 1 to 20, and d is 0 or 1, where a and b will not be 0 at the same time)

對苯二胺、4,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基硫醚、4-胺基苯基-4'-胺基苯甲酸酯、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'-二胺基二苯基醚、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'-(對伸苯基二亞異丙基)雙苯胺、4,4'-(間伸苯基二亞異丙基)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、3,6-二胺基咔唑、N-甲基-3,6-二胺基咔唑、N-乙基-3,6-二胺基咔唑、N-苯基-3,6-二胺基咔唑、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)-哌嗪、3,5-二胺基苯甲酸等其他二胺等；二胺基有機矽氧烷例如可列舉：1,3-雙(3-胺基丙基)-四甲基二矽氧烷等；除此以外，還可使用日本專利特開2010-97188號公報中記載的二胺。二胺可將所述二胺的1種單獨使用或者將2種以上組合使用。 P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4'-aminobenzoate, 1 2,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diamine Benzene, 2,7-diaminophosphonium, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9- Bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro Propane, 4,4 '-(p-phenylene diisopropylidene) bisaniline, 4,4'-(m-phenylene diisopropylidene) bisaniline, 1,4-bis (4-amino (Phenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine , 3,6-diaminoacridine, 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) -piperazine, 3,5-diaminobenzoic acid and other diamines; etc .; diamine organosiloxane For example 1,3-bis (3-amino-propyl) - tetramethyl siloxane silicon and the like; in addition, may also be used Laid-Open Japanese Patent Application Publication No. 2010-97188 diamine described. The diamine may be used singly or in combination of two kinds. Use in combination.

所述式(D-1)中的「-X^I-(R^I-X^II)_n-」所表示的2價基優選為：碳數1~3的烷二基、*-O-、*-COO-或者*-O-C₂H₄-O-(其中，標注有「*」的結合鍵與二胺基苯基鍵結)。基團「-C_cH_2c+1」的具體例可列舉例如：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個胺基優選為相對於其他基團而位於2,4-位或者3,5-位。 The divalent group represented by "-X ^I- (R ^I -X ^II ) _n- " in the formula (D-1) is preferably an alkanediyl group having 1 to 3 carbon atoms, * -O-, * -COO- or * -OC ₂ H ₄ -O- (wherein the bond marked with "*" is bonded to the diaminophenyl group). Specific examples of the group "-C _c H _{2c + 1} " include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-nonyl , N-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-19 Alkyl, n-icosyl and the like. The two amino groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position with respect to the other groups.

所述式(a-1)所表示的化合物的具體例可列舉例如下述式(a-1-1)~式(a-1-3)分別所表示的化合物等。 Specific examples of the compound represented by the formula (a-1) include, for example, compounds represented by the following formulae (a-1-1) to (a-1-3).

<聚醯胺酸的合成> <Synthesis of Polyamic Acid>

聚醯胺酸可通過使如上所述的四羧酸二酐與二胺，視需要與封端劑一起進行反應而獲得。提供給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為相對於二胺的胺基1當量，四羧酸二酐的酸酐基成為0.2當量~2當量的比例，更優選為成為0.3 當量~1.2當量的比例。 Polyamic acid can be obtained by reacting the tetracarboxylic dianhydride and diamine as described above with an end-capping agent as necessary. The use ratio of the tetracarboxylic dianhydride and the diamine provided for the synthesis reaction of the polyamic acid is preferably 1 equivalent to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride becomes a ratio of 0.2 to 2 equivalents. More preferably 0.3 Equivalent to 1.2 equivalent.

所述封端劑例如可列舉：順丁烯二酸酐、鄰苯二甲酸酐、衣康酸酐等酸單酐，苯胺、環己胺、正丁胺等單胺化合物，異氰酸苯基酯、異氰酸萘基酯等單異氰酸酯化合物等。相對於所使用的四羧酸二酐以及二胺的合計100重量份，封端劑的使用比例優選為設為20重量份以下，更優選為設為10重量份以下。 Examples of the blocking agent include acid monoanhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, phenyl isocyanate, Monoisocyanate compounds such as naphthyl isocyanate and the like. The use ratio of the blocking agent 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 tetracarboxylic dianhydride and diamine used.

聚醯胺酸的合成反應優選為在有機溶劑中進行。此時的反應溫度優選為-20℃~150℃，更優選為0℃~100℃。另外，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 the polyamic acid is preferably performed 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. The reaction time is preferably from 0.1 to 24 hours, and more preferably from 0.5 to 12 hours.

反應中使用的有機溶劑例如可列舉：非質子性極性溶劑、酚系溶劑、醇、酮、酯、醚、鹵化烴、烴等。這些有機溶劑中，優選為使用選自由非質子性極性溶劑以及酚系溶劑所組成的組群(第一組群的有機溶劑)中的1種以上，或者選自第一組群的有機溶劑中的1種以上與選自由醇、酮、酯、醚、鹵化烴及烴所組成的組群(第二組群的有機溶劑)中的1種以上的混合物。在後一種情況下，相對於第一組群的有機溶劑以及第二組群的有機溶劑的合計量，第二組群的有機溶劑的使用比例優選為50重量%以下，更優選為40重量%以下，尤其優選為30重量%以下。 Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenol-based solvent (organic solvent of the first group), or an organic solvent selected from the first group is preferably used. And a mixture of one or more kinds selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (organic solvents of the second group). In the latter case, the use ratio of the organic solvent in the second group is preferably 50% by weight or less, and more preferably 40% by weight, with respect to the total amount of the organic solvent in the first group and the organic solvent in the second group. Hereinafter, it is particularly preferably 30% by weight or less.

特別優選為使用選自由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、間甲酚、二甲酚以及鹵化苯酚所組成的組群中的1種以上作為溶劑，或者優選為在所述比例的範圍內使用所述溶劑的1種以上與其他有機溶劑的混合物。 It is particularly preferable to use a member selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylmethylene, γ-butyrolactone, One or more of the group consisting of methylurea, hexamethylphosphonium triamine, m-cresol, xylenol and halogenated phenol are used as a solvent, or it is preferable to use the above within the range of the ratio A mixture of one or more solvents with other organic solvents.

有機溶劑的使用量(a)優選為設為相對於反應溶液的總量(a+b)，四羧酸二酐以及二胺的合計量(b)成為0.1重量%~50重量%的量。 The amount of the organic solvent used (a) is preferably set relative to that of the reaction solution. The total amount (a + b) and the total amount (b) of tetracarboxylic dianhydride and diamine are 0.1 to 50% by weight.

如以上所述，獲得將聚醯胺酸溶解而成的反應溶液。該反應溶液可直接提供給液晶配向劑的製備，也可以將反應溶液中所含的聚醯胺酸離析後再提供給液晶配向劑的製備，或者還可以將所離析的聚醯胺酸進行純化後再提供給液晶配向劑的製備。聚醯胺酸的離析以及純化可依據公知的方法來進行。 As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The The reaction solution may be directly provided to the preparation of the liquid crystal alignment agent, or the polyamidic acid contained in the reaction solution may be isolated and then provided to the preparation of the liquid crystal alignment agent, or the isolated polyamidic acid may be purified It is then provided for the preparation of the liquid crystal alignment agent. Isolation and purification of polyamic acid can be performed according to a known method.

<聚醯胺酸酯> <Polyurethane>

本發明的聚醯胺酸酯例如可利用以下方法來獲得：[I]通過使由所述合成反應而獲得的聚醯胺酸與含羥基的化合物、鹵化物、含環氧基的化合物等進行反應來合成的方法；[II]使四羧酸二酯與二胺進行反應的方法；[III]使四羧酸二酯二鹵化物與二胺進行反應的方法等。 The polyamidate of the present invention can be obtained, for example, by the following method: [I] The polyamino acid obtained by the synthesis reaction is performed with a hydroxyl-containing compound, a halide, an epoxy-containing compound, or the like. A method for synthesizing by reaction; [II] a method for reacting a tetracarboxylic acid diester with a diamine; [III] a method for reacting a tetracarboxylic acid diester dihalide with a diamine, and the like.

此處，方法[I]中使用的含羥基的化合物例如可列舉：甲醇、乙醇、丙醇等醇類；苯酚、甲酚等酚類等。另外，鹵化物例如可列舉：溴代甲烷、溴代乙烷、溴代十八烷、氯代甲烷、氯代十八烷、1,1,1-三氟-2-碘乙烷等，含環氧基的化合物例如可列舉環氧丙烷等。 Here, examples of the hydroxyl-containing compound used in the method [I] include alcohols such as methanol, ethanol, and propanol; and phenols such as phenol and cresol. Examples of the halide include bromomethane, bromoethane, bromooctadecane, methyl chloride, octadecane chloride, 1,1,1-trifluoro-2-iodoethane, and the like. Examples of the epoxy-based compound include propylene oxide.

方法[II]中使用的四羧酸二酯例如可通過使用所述醇類，將所述聚醯胺酸的合成中所例示的四羧酸二酐進行開環而獲得。方法[II]的反應優選為在適當的脫水催化劑的存在下進行。脫水催化劑例如可列舉：4-(4,6-二甲氧基-1,3,5-三嗪-2-基)-4-甲基嗎啉正離子鹵化物、羰基咪唑、磷系縮合劑等。方法[III]中使用的四羧酸二酯二鹵化物可通過使例如以所述方式獲得的四羧酸二酯、與亞硫醯氯等適當的氯化劑進行反應而獲得。 The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by using the alcohols to ring-open the tetracarboxylic dianhydride illustrated in the synthesis of the polyamic acid. Got. The reaction of the method [II] is preferably performed in the presence of a suitable dehydration catalyst. Examples of the dehydration catalyst include 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholine positive ion halide, carbonylimidazole, and phosphorus-based condensation agent. Wait. The tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting, for example, the tetracarboxylic acid diester obtained in the manner described above with an appropriate chlorinating agent such as thionyl chloride.

方法[II]及方法[III]中使用的二胺可列舉聚醯胺酸的合成中所例示的二胺。此外，聚醯胺酸酯可僅具有醯胺酸酯結構，也可以是醯胺酸結構與醯胺酸酯結構並存的部分酯化物。 Examples of the diamine used in the method [II] and the method [III] include a combination of polyamines. The exemplified diamine. In addition, the polyamidate may have only a pseudoamidate structure, or may be a partially esterified product in which a pseudoamidate structure and a pseudoamidate structure coexist.

<聚醯亞胺> <Polyimide>

本發明的液晶配向劑中所含有的聚醯亞胺可通過將例如以所述方式合成的聚醯胺酸進行脫水閉環，加以醯亞胺化而獲得。 The polyfluorene imide contained in the liquid crystal alignment agent of the present invention can be obtained by, for example, dehydrating and closing the polyphosphonic acid synthesized in the manner described above, and then fluorinating the polyimide.

所述聚醯亞胺可以是將作為其前驅物的聚醯胺酸所具有的全部醯胺酸結構進行脫水閉環而成的完全醯亞胺化物，也可以是僅將醯胺酸結構的一部分進行脫水閉環，使醯胺酸結構與醯亞胺環結構並存的部分醯亞胺化物。就電特性的觀點而言，本發明的聚醯亞胺的醯亞胺化率優選為30%以上，更優選為50%~99%，尤其優選為65%~99%。該醯亞胺化率是相對於聚醯亞胺的醯胺酸結構的數量與醯亞胺環結構的數量的合計，將醯亞胺環結構的數量所占的比例以百分率進行表示。此處，醯亞胺環的一部分可以是異醯亞胺環。 The polyimide may be a complete amidine compound obtained by dehydrating and ring-closing all the amidine structures of the polyamidate which is a precursor thereof, or may be a process in which only a part of the amidine structure is carried out. Dehydration ring closure, part of the fluorinated imine compound of the fluorinated amino acid structure and the fluorinated imine ring structure. From the viewpoint of electrical characteristics, the polyimide ratio of the polyimide of the present invention is preferably 30% or more, more preferably 50% to 99%, and particularly preferably 65% to 99%. The fluorene imidization ratio is a total of the number of fluorene imine structures and the number of fluorene imine rings relative to the number of fluorene imine structures of polyfluorene, and the ratio of the number of fluorene imine rings is expressed as a percentage. Here, a part of the fluorene imine ring may be an isofluorene ring.

聚醯胺酸的脫水閉環優選為利用以下方法來進行：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，在該溶液中添加脫水劑以及脫水閉環催化劑，視需要進行加熱的方法。其中，優選為利用後一種方法。 The dehydration ring closure of the polyamic acid is preferably performed by a method of heating the polyamino acid, or dissolving the polyamino acid in an organic solvent, and A method in which a dehydrating agent and a dehydration ring-closing catalyst are added to the solution, and heating is performed if necessary. Among these, the latter method is preferably used.

在所述聚醯胺酸的溶液中添加脫水劑以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。脫水劑的使用量優選為相對於聚醯胺酸的醯胺酸結構的1莫耳而設為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。脫水閉環催化劑的使用量優選為相對於所使用的脫水劑1莫耳而設為0.01莫耳~10莫耳。脫水閉環反應中使用的有機溶劑可列舉用於合成聚醯胺酸的有機溶劑。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。 Adding a dehydrating agent and a dehydration ring-closing catalyst to the solution of the polyamic acid In the method of converting the agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. The used amount of the dehydrating agent is preferably 0.01 mol to 20 mol with respect to 1 mol of the sulfamic acid structure of the polyamic acid. Examples of the dehydration ring-closing catalyst include tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine. The used amount of the dehydration ring-closing catalyst is preferably 0.01 to 10 mols with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closing reaction include organic solvents used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 ° C to 180 ° C, and more preferably 10 ° C to 150 ° C. The reaction time is preferably 1.0 to 120 hours, and more preferably 2.0 to 30 hours.

以所述方式獲得含有聚醯亞胺的反應溶液。該反應溶液可直接提供給液晶配向劑的製備，也可以自反應溶液中去除脫水劑以及脫水閉環催化劑後再提供給液晶配向劑的製備，也可以將聚醯亞胺離析後再提供給液晶配向劑的製備，或者還可以將所離析的聚醯亞胺進行純化後再提供給液晶配向劑的製備。這些純化操作可依據公知的方法來進行。 In this way, a reaction solution containing polyfluoreneimine was obtained. The reaction solution Can be directly provided to the preparation of liquid crystal alignment agent, or can be provided to the preparation of liquid crystal alignment agent after removing the dehydrating agent and dehydration ring-closing catalyst from the reaction solution, or the polyfluorene imide can be provided to the preparation of liquid crystal alignment agent Or, the isolated polyfluorene imide can be purified and then provided to the preparation of the liquid crystal alignment agent. These purification operations can be performed according to a known method.

以所述方式獲得的聚醯胺酸、聚醯胺酸酯以及聚醯亞胺優選為當將其製成濃度為10重量%的溶液時，具有10mPa．s~800mPa．s的溶液黏度，更優選為具有15mPa．s~500mPa．s的溶液黏度。此外，所述聚合物的溶液黏度(mPa．s)是對於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)來製備的濃度為10重量%的聚合物溶液，使用E型旋轉黏度計，在25℃下測定而得的值。對於聚醯胺酸、聚醯胺酸酯以及聚醯亞胺，利用凝膠滲透層析法來測定的聚苯乙烯換算的重量平均分子量優選為1,000~500,000，更優選為2,000~300,000。 Polyamidic acid, polyamidate, and polyimide obtained in the manner described When it is made into a solution with a concentration of 10% by weight, it preferably has 10 mPa. s ~ 800mPa. The solution viscosity of s is more preferably 15 mPa. s ~ 500mPa. Solution viscosity of s. In addition, the solution viscosity (mPa.s) of the polymer is for the use of the polymer A good solvent (such as γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) is a value obtained by measuring a polymer solution at a concentration of 10% by weight using an E-type rotary viscometer at 25 ° C. . As for polyamic acid, a polyamic acid ester, and a polyimide, the polystyrene equivalent weight average molecular weight measured by the gel permeation chromatography method is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000.

<聚有機矽氧烷> <Polyorganosiloxane>

本發明的液晶配向劑中所含有的聚有機矽氧烷只要是具有矽氧烷骨架的聚有機矽氧烷即可，側鏈部分的結構並無特別限定。就與化合物(D)所具有的基團「A2」進行反應來提高液晶配向性及液晶穩定性的觀點而言，優選為包含具有環氧基的聚有機矽氧烷(以下也稱為「含環氧基的聚有機矽氧烷」)。含環氧基的聚有機矽氧烷的具體例可列舉例如具有下述式(S-1)所表示的重複單元的聚有機矽氧烷、其水解物或者水解物的縮合物等。 The polyorganosiloxane contained in the liquid crystal alignment agent of the present invention may be a polyorganosiloxane having a siloxane skeleton, and the structure of the side chain portion is not particularly limited. From the viewpoint of improving the liquid crystal alignment and liquid crystal stability by reacting with the group "A2" possessed by the compound (D), it is preferable to include a polyorganosiloxane having an epoxy group (hereinafter also referred to as "containing Epoxy polyorganosiloxane "). Specific examples of the epoxy-group-containing polyorganosiloxane include a polyorganosiloxane having a repeating unit represented by the following formula (S-1), a hydrolyzate thereof, or a condensate of the hydrolyzate.

(式(S-1)中，X¹為具有環氧基的1價有機基，Y¹為羥基、碳數1~10的烷基、碳數1~10的烷氧基或者碳數6~20的芳基；分子內的X¹、Y¹可相互相同，也可以不同。) (In the formula (S-1), X ¹ is a monovalent organic group having an epoxy group, and Y ¹ is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. Aryl of 20; X ¹ and Y ^{1 in the} molecule may be the same or different from each other.)

式(S-1)中的X¹只要具有環氧基，則其餘的結構並無特別限定，例如可列舉：在鏈狀烴基、脂環式烴基或者芳香族烴基上鍵結有環氧基而成的基團等。X¹的優選具體例可列舉例如下述式(X1-1)~式(X1-3)分別所表示的基團等。 As long as X ¹ in the formula (S-1) has an epoxy group, the remaining structure is not particularly limited, and examples thereof include an epoxy group bonded to a chain hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. Into a group. Preferable specific examples of X ¹ include, for example, groups represented by the following formulae (X1-1) to (X1-3).

(式中，「*」表示與矽原子的結合鍵。) (In the formula, "*" represents a bond with a silicon atom.)

此外，本說明書中的所謂「鏈狀烴基」，是指在主鏈上不包含環狀結構，而僅由鏈狀結構所構成的直鏈狀烴基以及分支狀烴基。所謂「脂環式烴基」，是指僅包含脂環式烴的結構作為環結構，而不包含芳香環結構的烴基。其中，不需要僅由脂環式烴的結構所構成，也包含在其一部分中具有鏈狀結構的烴基。所謂「芳香族烴基」，是指包含芳香環結構作為環結構的烴基。其中，不需要僅由芳香環結構所構成，也可以在其一部分中包含鏈狀結構或脂環式烴的結構。 In addition, the "chain hydrocarbon group" in this specification means a straight-chain hydrocarbon group and a branched hydrocarbon group which are not comprised of a cyclic structure in a main chain, but are comprised only of a chain structure. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. However, it is not necessary to consist only of the structure of an alicyclic hydrocarbon, and it is also necessary to include the hydrocarbon group which has a chain structure in a part. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not need to consist only of an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in part.

式(S-1)中的Y¹的碳數1~10的烷基例如可列舉：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等，這些烴基可以是直鏈狀，也可以是分支狀。Y¹的碳數1~10的烷氧基例如可列舉所述烷基與氧原子鍵結而成的基團，具體而言可列舉甲氧基、乙氧基等。碳數6~20的芳基例如可列舉苯基、苄基、甲苯基等。 Examples of the alkyl group having 1 to 10 carbon atoms of Y ¹ in the formula (S-1) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. These hydrocarbon groups may be linear or branched. Examples of the alkoxy group having 1 to 10 carbon atoms of Y ¹ include a group in which the alkyl group is bonded to an oxygen atom, and specific examples thereof include a methoxy group and an ethoxy group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a benzyl group, and a tolyl group.

含環氧基的聚有機矽氧烷的環氧當量優選為100g/莫耳~10,000g/莫耳，更優選為150g/莫耳~1,000g/莫耳。 The epoxy equivalent of the epoxy group-containing polyorganosiloxane is preferably 100 g / mole to 10,000 g / mole, and more preferably 150 g / mole to 1,000 g / mole.

含環氧基的聚有機矽氧烷的利用凝膠滲透層析法來測定的聚苯乙烯換算的重量平均分子量優選為500~100,000，更優選為1,000~10,000，尤其優選為1,000~5,000。 The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of the epoxy-containing polyorganosiloxane is preferably 500 to 100,000, more preferably 1,000 to 10,000, and particularly preferably 1,000 to 5,000.

<聚有機矽氧烷的合成> <Synthesis of Polyorganosiloxane>

如上所述的含環氧基的聚有機矽氧烷例如可通過將具有環氧基的水解性矽烷化合物(含環氧基的矽烷化合物)、或者該含環氧基的矽烷化合物與其他的矽烷化合物的混合物，優選為在適當的有機溶劑、水以及催化劑的存在下進行水解以及縮合而獲得。 The above-mentioned epoxy-group-containing polyorganosiloxane can be obtained by, for example, combining a hydrolyzable silane compound (epoxy group-containing silane compound) having an epoxy group, or the epoxy group-containing silane compound and another silane The mixture of compounds is preferably obtained by hydrolysis and condensation in the presence of a suitable organic solvent, water, and a catalyst.

所述含環氧基的矽烷化合物例如可列舉：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、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基二甲基甲氧基矽烷、3-縮水甘油氧基丙基二甲基乙氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、2-(3,4-環氧基環己基)乙基三乙氧基矽烷等。含環氧基的矽烷化合物可單獨使用1種或者將2種以上混合使用。 Examples of the epoxy-containing silane compound include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyl Dimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethyl Oxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like. The epoxy group-containing silane compound may be used singly or in combination of two or more kinds.

所述其他的矽烷化合物只要為水解性，則並無特別限定，例如可列舉：甲基三氯矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、苯基三氯矽烷、苯基三甲氧基矽烷、甲基二氯矽烷、甲基二甲氧基矽烷、二甲基二氯矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二苯基二氯矽烷、二苯基二甲氧基矽烷、甲氧基二甲基矽烷、乙氧基二甲基矽烷、氯三甲基矽烷、溴三甲基矽烷、碘三甲基矽烷、甲氧基三甲基矽烷、乙氧基三甲基矽烷、四甲氧基矽烷、四乙氧基矽烷、十八烷基三氯矽烷、十八烷基三甲氧基矽烷、乙烯基三氯矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、烯丙基三甲氧基矽烷、烯丙基三乙氧基矽烷；3-(甲基)丙烯醯氧基丙基三氯矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、2-(甲基)丙烯醯氧基乙基三氯矽烷、2-(甲基)丙烯醯氧基乙基三甲氧基矽烷、2-(甲基)丙烯醯氧基乙基三乙氧基矽烷、4-(甲基)丙烯醯氧基丁基三氯矽烷、4-(甲基)丙烯醯氧基丁基三甲氧基矽烷、4-(甲基)丙烯醯氧基丁基三乙氧基矽烷、3-(甲基)丙烯醯氧基丁基三甲氧基矽烷、3-(甲基)丙烯醯氧基戊基三甲氧基矽烷、3-(甲基)丙烯醯氧基己基三甲氧基矽烷、3-(甲基)丙烯醯氧基庚基三甲氧基矽烷、3-(甲基)丙烯醯氧基辛基三甲氧基矽烷、3-(甲基)丙烯醯氧基壬基三甲氧基矽烷、3-(甲基)丙烯醯氧基癸基三甲氧基矽烷、3-(甲基)丙烯醯氧基十一烷基三甲氧基矽烷、3-(甲基)丙烯醯氧基十二烷基三甲氧基矽烷等。其他的矽烷化合物可單獨使用1種，也可以將2種以上組合使用。此外，「(甲基)丙烯醯氧基」為包含「丙烯醯氧基」以及「甲基丙烯醯氧基」的含意。 The other silane compounds are not particularly limited as long as they are hydrolyzable. Examples include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrichlorosilane, and phenyl. Trimethoxysilane, methyldichlorosilane, methyldimethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethoxysilane Methyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethyl Silane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, tetramethoxysilane, tetraethoxysilane, octadecyltrichlorosilane, octadecyltrimethoxy Silane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane; 3- (meth) acrylic acid Propyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2- (meth) acrylic acid Oxyethyltrichlorosilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 4- (meth) propylene Ethoxybutyltrichlorosilane, 4- (meth) acrylic ethoxybutyltrimethoxysilane, 4- (meth) acrylic ethoxybutyltriethoxysilane, 3- (methyl) Propylene methoxybutyltrimethoxysilane, 3- (meth) propenyloxypentyltrimethoxysilane, 3- (meth) propenyloxyhexyltrimethoxysilane, 3- (meth) propenyloxyheptyltrimethoxysilane, 3- (meth) propenyloxyoctyltrimethoxysilane, 3- (meth) propenyloxynonyltrimethoxysilane, 3- (meth) propenyloxydecyltrimethoxysilane , 3- (meth) propenyloxy undecyltrimethoxysilane, 3- (meth) propenyloxydodecyltrimethoxysilane, and the like. The other silane compounds may be used singly or in combination of two or more kinds. In addition, "(meth) acryloxy" means the meaning of "acryloxy" and "methacryloxy".

所述含環氧基的聚有機矽氧烷的合成中，優選為以所得的聚有機矽氧烷的環氧當量成為所述的優選範圍的方式，來調整所述含環氧基的矽烷化合物與其他矽烷化合物的使用比例。 In the synthesis of the epoxy-group-containing polyorganosiloxane, it is preferable to adjust so that the epoxy equivalent of the obtained polyorganosiloxane becomes the above-mentioned preferred range. The ratio of the epoxy-containing silane compound to other silane compounds.

聚有機矽氧烷的合成時可使用的有機溶劑例如可列舉：烴、酮、酯、醚、醇等。此處，所述烴例如可列舉甲苯、二甲苯等；所述酮例如可列舉：甲基乙基酮、甲基異丁基酮、甲基正戊基酮、二乙基酮、環己酮等；所述酯例如可列舉：乙酸乙酯、乙酸正丁酯、乙酸異戊酯、丙二醇單甲醚乙酸酯、3-甲氧基丁基乙酸酯、乳酸乙酯等；所述醚例如可列舉：乙二醇二甲醚、乙二醇二***、四氫呋喃、二噁烷等；所述醇例如可列舉：1-己醇、4-甲基-2-戊醇、乙二醇單甲醚、乙二醇單***、乙二醇單-正丙醚、乙二醇單-正丁醚、丙二醇單甲醚、丙二醇單***、丙二醇單-正丙醚等。這些有機溶劑中，優選為使用非水溶性的有機溶劑。此外，這些有機溶劑可單獨使用1種或者將2種以上混合使用。 Examples of organic solvents that can be used in the synthesis of polyorganosiloxanes are listed below. Examples: hydrocarbons, ketones, esters, ethers, alcohols, etc. Here, examples of the hydrocarbon include toluene and xylene; examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, and cyclohexanone Examples of the ester include ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, and the like; Examples include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, and the like; examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, and ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and the like. Among these organic solvents, a water-insoluble organic solvent is preferably used. These organic solvents may be used singly or in combination of two or more.

相對於合成中使用的全部矽烷化合物100重量份，合成所述聚有機矽氧烷的情況下的有機溶劑的使用量優選為10重量份~10,000重量份，更優選為50重量份~1,000重量份。另外，相對於合成中使用的全部矽烷化合物，合成所述聚有機矽氧烷時的水的使用量優選為0.5倍莫耳~100倍莫耳，更優選為1倍莫耳~30倍莫耳。 Based on 100 parts by weight of all silane compounds used in the synthesis, The use amount of the organic solvent in the case of the polyorganosiloxane is preferably 10 parts by weight to 10,000 parts by weight, and more preferably 50 parts by weight to 1,000 parts by weight. In addition, the amount of water used in synthesizing the polyorganosiloxane is preferably 0.5 to 100 times mol, and more preferably 1 to 30 times mol, relative to all the silane compounds used in the synthesis. .

合成所述聚有機矽氧烷時可使用的催化劑例如可列舉：酸、鹼金屬化合物、有機鹼、鈦化合物、鋯化合物等。此處，所述酸例如可列舉：鹽酸、硫酸、硝酸、甲酸、乙二酸、乙酸、三氟乙酸、三氟甲磺酸、磷酸等；所述鹼金屬化合物例如可列舉：氫氧化鈉、氫氧化鉀、甲醇鈉、甲醇鉀、乙醇鈉、乙醇鉀等；所述有機鹼例如可列舉：乙胺、二乙胺、哌嗪、哌啶、吡咯烷、吡咯之類的一級有機胺~二級有機胺，三乙胺、三-正丙胺、三-正丁胺、吡啶、4-二甲基胺基吡啶、二氮雜雙環十一烯之類的三級有機胺，氫氧化四甲基銨之類的四級有機胺等。 Examples of the catalyst that can be used in the synthesis of the polyorganosiloxane are listed below. Examples: acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, etc. Here, examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and phosphoric acid. Examples of the alkali metal compound include: Sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like; examples of the organic base include ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole. Organic amines ~ secondary organic amines, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene and other tertiary organic amines, hydrogen Tertiary organic amines such as tetramethylammonium oxide.

所述催化劑特別優選為有機鹼。有機鹼的使用量根據有機鹼的種類、溫度等反應條件等而不同，可適當地設定，但例如相對於全部矽烷化合物，優選為0.01倍莫耳~3倍莫耳，更優選為0.05倍莫耳~1倍莫耳。 The catalyst is particularly preferably an organic base. The amount of organic base used is based on The type of organic base, reaction conditions such as temperature, and the like can be appropriately set, but, for example, it is preferably 0.01 to 3 times mole, and more preferably 0.05 to 1 mole. .

合成所述聚有機矽氧烷時的水解．縮合反應優選為通過如下操作來實施：將水解性矽烷化合物的1種或者2種以上溶解於有機溶劑中，將所得的溶液與有機鹼及水混合，例如利用油浴等來進行加熱。 Hydrolysis during synthesis of the polyorganosiloxane. The condensation reaction is preferably carried out by This is carried out by dissolving one or two or more types of hydrolyzable silane compounds in an organic solvent, mixing the obtained solution with an organic base and water, and heating the oil bath or the like, for example.

水解．縮合反應時，理想的是將加熱溫度設為優選為 130℃以下、更優選為40℃~100℃，進行優選為0.5小時~12小時、更優選為1小時~8小時的加熱。加熱中，可將混合液進行攪拌，也可以放置在回流下。 hydrolysis. In the condensation reaction, it is desirable to set the heating temperature to preferably 130 ° C. or lower, more preferably 40 ° C. to 100 ° C., and heating is preferably performed for 0.5 to 12 hours, and more preferably 1 to 8 hours. During heating, the mixed solution may be stirred or may be left under reflux.

反應結束後，優選為利用水對自反應液中分取的有機溶劑層進行洗滌。該洗滌時，通過使用包含少量鹽的水，例如0.2重量%左右的硝酸銨水溶液等進行洗滌，就洗滌操作變得容易的方面而言優選。洗滌進行至洗滌後的水層成為中性為止，然後視需要以無水硫酸鈣、分子篩等乾燥劑，將有機溶劑層乾燥後，去除溶劑，由此獲得作為目標的聚有機矽氧烷。此外，所述含環氧基的聚有機矽氧烷也可以使用市售品。所述市售品例如可列舉DMS-E01、DMS-E12、DMS-E21、EMS-32(以上由智索(Chisso)(股)製造)等。 After the reaction is completed, it is preferable to use water to dissolve the organic solvent separated from the reaction solution. The agent layer was washed. In this washing, washing with water containing a small amount of salt, for example, about 0.2% by weight of an ammonium nitrate aqueous solution, or the like is preferred in terms of ease of washing operation. The washing is performed until the washed aqueous layer becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieve, if necessary, and then removed. A solvent, whereby a target polyorganosiloxane is obtained. Moreover, the said epoxy group containing polyorganosiloxane can also use a commercial item. Examples of the commercially available product include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (the above are manufactured by Chisso).

本發明的液晶配向劑中所含有的聚有機矽氧烷可優選使用具有可對塗膜賦予液晶配向能力的基團(以下也稱為「液晶配向性基」)的化合物。具有液晶配向性基的聚有機矽氧烷(以下也稱為「含配向性基的聚有機矽氧烷」)可以是與含環氧基的聚有機矽氧烷分別含有的形態，或者也可以是作為具有環氧基及液晶配向性基的聚有機矽氧烷而含有的形態。優選為後者。含配向性基的聚有機矽氧烷的優選具體例可列舉例如具有下述式(S-2)所表示的重複單元的聚有機矽氧烷等。 The polyorganosiloxane contained in the liquid crystal alignment agent of the present invention is preferably A compound having a group capable of imparting a liquid crystal alignment ability to a coating film (hereinafter also referred to as a "liquid crystal alignment group") is used. The polyorganosiloxane having a liquid crystal alignment group (hereinafter also referred to as "polyorganosiloxane containing an alignment group") may be in the form of being separately contained from the polyorganosiloxane containing an epoxy group, or it may be It is a form contained as a polyorganosiloxane having an epoxy group and a liquid crystal alignment group. The latter is preferred. Preferred specific examples of the polyorganosiloxane containing an alignment group include polyorganosiloxane having a repeating unit represented by the following formula (S-2).

(式(S-2)中，X²為具有液晶配向性基的1價有機基；Y¹與所述式(S-1)含意相同。) (In the formula (S-2), X ² is a monovalent organic group having a liquid crystal alignment group; Y ¹ has the same meaning as the formula (S-1).)

式(S-2)中的X²只要具有液晶配向性基，則其餘的結構並無特別限定。X²的優選具體例可列舉例如下述式(X2-1A)~式(X2-3B)分別所表示的基團等。 As long as X ² in the formula (S-2) has a liquid crystal alignment group, the remaining structure is not particularly limited. Preferred specific examples of X ² include, for example, groups represented by the following formulae (X2-1A) to (X2-3B).

(式中，R³為液晶配向性基；「*」表示與矽原子的結合鍵。) (In the formula, R ³ is a liquid crystal alignment group; "*" represents a bonding bond with a silicon atom.)

液晶配向性基(R³)可列舉：通過光異構化或光二聚化、光分解等而顯示出光配向性的基團(以下也稱為「光配向性基」)、可對塗膜賦予預傾角特性的基團(以下也稱為「預傾角賦予基」)等。 Examples of the liquid crystal alignment group (R ³ ) include a group that exhibits photoalignment by photoisomerization, photodimerization, and photodecomposition (hereinafter also referred to as "photoalignment group"), and can be given to a coating film. A group having a pretilt angle characteristic (hereinafter also referred to as a "pretilt angle imparting group") and the like.

在利用光配向法來進行對塗膜賦予液晶配向能力的處理的情況下，優選為包含具有光配向性基的聚有機矽氧烷。光配向性基可採用來源於通過光異構化或光二聚化、光分解等而顯示出配向性的各種化合物的基團，例如可列舉：含有偶氮苯或其衍生物作為基本骨架的含偶氮苯的基團、含有肉桂酸或其衍生物作為基本骨架的具有肉桂酸結構的基團、含有查耳酮或其衍生物作為基本骨架的含查耳酮的基團、含有二苯甲酮或其衍生物作為基本骨架的含二苯甲酮的基團、含有香豆素或其衍生物作為基本骨架的含香豆素的基團等。其中，就光配向性良好的方面以及容易導入至聚合物中的方面而言，優選為具有肉桂酸結構的基團。 When the process of providing liquid crystal alignment ability to a coating film is performed by the photo-alignment method, it is preferable to contain the polyorganosiloxane which has a photo-alignment group. The photo-alignment group may be a group derived from various compounds exhibiting alignment by photoisomerization, photodimerization, photodecomposition, or the like. Examples include groups containing azobenzene or a derivative thereof as a basic skeleton. Azobenzene group, cinnamic acid structure group containing cinnamic acid or its derivative as basic skeleton, chalcone group containing chalcone or its derivative as basic skeleton, dibenzoyl group A benzophenone-containing group having a ketone or a derivative thereof as a basic skeleton, a coumarin-containing group containing a coumarin or a derivative thereof as a basic skeleton, and the like. Among these, a group having a cinnamic acid structure is preferred in terms of good photo-alignment and easy introduction into a polymer.

所述式(S-2)的R³為光配向性基的聚有機矽氧烷例如可通過使所述獲得的含環氧基的聚有機矽氧烷、與具有光配向性基的羧酸(C-1)進行反應而獲得。所述羧酸(C-1)的優選例可列舉例如下述式(C1-1)~式(C1-3)分別所表示的化合物等。 The polyorganosiloxane in which R ^{3 in} the formula (S-2) is a photo-alignment group can be obtained by, for example, obtaining the obtained polyorganosiloxane containing an epoxy group and a carboxylic acid having a photo-alignment group. (C-1) Obtained by performing a reaction. Preferable examples of the carboxylic acid (C-1) include, for example, compounds represented by the following formulae (C1-1) to (C1-3).

(式中，R⁸及R¹¹分別獨立地為氫原子、碳數1~20的烷基或者該烷基中的至少1個氫原子經氟原子或氰基所取代的基團；R⁶、R⁷及R⁹分別獨立地為1,4-伸環己基或1,4-伸苯基；R¹⁰為碳數2~10的烷二基；Z¹、Z²、Z³、Z⁴及Z⁵分別獨立地為單鍵、醚基、硫醚基、酯基或者硫酯基；s、t及u分別獨立地為0或1。) (Wherein R ⁸ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group in which at least one hydrogen atom in the alkyl group is substituted with a fluorine atom or a cyano group; R ⁶ , R ⁷ and R ⁹ are independently 1,4-cyclohexyl or 1,4-phenylene; R ¹⁰ is an alkyldiyl group having 2 to 10 carbon atoms; Z ¹ , Z ² , Z ³ , Z ⁴ and Z ^{5 is} independently a single bond, an ether group, a thioether group, an ester group, or a thioester group; s, t, and u are each independently 0 or 1.)

R⁸及R¹¹的碳數1~20的烷基可以是直鏈狀，也可以是分支狀，但優選為直鏈狀。所述式(C1-1)的優選具體例可列舉例如下述式(c1-1-1)~式(c1-1-10)分別所表示的化合物等；所述式(C1-2)的優選具體例可列舉例如下述式(c1-2-1)所表示的化合物等；所述式(C1-3)的優選具體例可列舉例如下述式(c1-3-1)所表示的化合物等。 The alkyl group having 1 to 20 carbon atoms of R ⁸ and R ¹¹ may be linear or branched, but is preferably linear. Preferred specific examples of the formula (C1-1) include, for example, compounds represented by the following formulae (c1-1-1) to (c1-1-10), and the like; Examples of preferred specific examples include compounds represented by the following formula (c1-2-1). Examples of preferred specific examples of the formula (C1-3) include those represented by the following formula (c1-3-1). Compounds etc.

[化9] [Chemical 9]

(式中，R⁸、R¹⁰、R¹¹與所述式(C1-1)~式(C1-3)含意相同。) (In the formula, R ⁸ , R ¹⁰ , and R ¹¹ have the same meanings as the formulas (C1-1) to (C1-3).)

預傾角賦予基例如可列舉：碳數4~40的烷基、碳數4~40的氟烷基、碳數4~40的烷氧基、碳數17~51的具有類固醇骨架的基團、具有多環結構的基團等。 Examples of the pretilt imparting group include an alkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 4 to 40 carbon atoms, an alkoxy group having 4 to 40 carbon atoms, a group having a steroid skeleton with 17 to 51 carbon atoms, A group having a polycyclic structure and the like.

所述式(S-2)的R³為預傾角賦予基的聚有機矽氧烷例如可通過使所述獲得的含環氧基的聚有機矽氧烷、與具有預傾角賦予基的羧酸(C-2)進行反應而獲得。所述羧酸(C-2)的優選例可列舉例如下述式(C2-1)~式(C2-5)分別所表示的化合物等。 The polyorganosiloxane in which R ^{3 in} the formula (S-2) is a pretilt imparting group can be obtained by, for example, obtaining the obtained polyorganosiloxane containing an epoxy group and a carboxylic acid having a pretilt imparting group. (C-2) Obtained by performing a reaction. Preferable examples of the carboxylic acid (C-2) include, for example, compounds represented by the following formulae (C2-1) to (C2-5).

(式中，R²²為碳數4~20的烷基或者氟烷基；R¹²為氫原子或者碳數1~20的烷基或者氟烷基；R¹³及R¹⁵分別獨立地為1,4-伸環己基或1,4-伸苯基；R¹⁴為氫原子或者甲基；R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰及R²¹分別獨立地為碳數1~10的烷二基；Z⁶、Z⁷、Z⁸、Z⁹、Z¹⁰、Z¹¹、Z¹²、Z¹³及Z¹⁴分別獨立地為單鍵、醚基、硫醚基、酯基或者硫酯基；p為0~3的整數，q為0~2的整數，r為0或1。) (Wherein R ²² is an alkyl group or a fluoroalkyl group having 4 to 20 carbon atoms; R ¹² is a hydrogen atom or an alkyl group or a fluoroalkyl group having 1 to 20 carbon atoms; R ¹³ and R ¹⁵ are each independently 1, 4-cyclohexyl or 1,4-phenylene; R ¹⁴ is a hydrogen atom or a methyl group; R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ^20, and R ²¹ are each independently 1 to 10 carbon atoms Alkyl diyl; Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ are each independently a single bond, ether group, thioether group, ester group or thioester group ; P is an integer from 0 to 3, q is an integer from 0 to 2, and r is 0 or 1.)

R²²及R¹²的烷基可以是直鏈狀，也可以是分支狀，優選為直鏈狀。所述式(C2-1)的優選具體例可列舉例如下述式(c2-1-1)~式(c2-1-9)分別所表示的化合物等；所述式(C2-2)的優選具體例可列舉例如下述式(c2-2-1)~式(c2-2-7)分別所表示的化合物等；所述式(C2-3)的優選具體例可列舉例如下述式(c2-3-1) 所表示的化合物等；所述式(C2-4)的優選具體例可列舉例如下述式(c2-4-1)所表示的化合物等；所述式(C2-5)的優選具體例可列舉例如下述式(c2-5-1)所表示的化合物等。 The alkyl groups of R ²² and R ¹² may be linear or branched, and are preferably linear. Preferred specific examples of the formula (C2-1) include, for example, compounds represented by the following formulae (c2-1-1) to (c2-1-9), and the like: Preferred specific examples include, for example, compounds represented by the following formulae (c2-2-1) to (c2-2-7); and preferred specific examples of the formula (C2-3) include, for example, the following formulae Compounds represented by (c2-3-1) and the like; preferred specific examples of the formula (C2-4) include, for example, compounds represented by the following formula (c2-4-1); and the like (C2- Preferred specific examples of 5) include, for example, a compound represented by the following formula (c2-5-1).

(式中，R²²、R¹²、R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²¹分別與所述式(C2-1)~式(C2-5)含意相同。) (In the formula, R ²² , R ¹² , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ have the same meanings as the formulas (C2-1) to (C2-5), respectively.)

在製造垂直配向型的液晶顯示元件的情況下，優選為包含具有預傾角賦予基的聚有機矽氧烷作為聚合物成分。此外，具有預傾角賦予基的聚有機矽氧烷的合成方法並不限定於所述，例如也可以通過單體組成中包含具有預傾角賦予基的水解性矽烷化合物的聚合來合成。 When manufacturing a liquid crystal display element of a vertical alignment type, it is preferable to include a polyorganosiloxane having a pretilt angle imparting group as a polymer component. The method for synthesizing a polyorganosiloxane having a pretilt imparting group is not limited to the above, and it may be synthesized by, for example, polymerizing a hydrolyzable silane compound having a pretilt imparting group in a monomer composition.

本發明的液晶配向劑中所含有的聚有機矽氧烷也可以使用具有聚合性不飽和基的聚有機矽氧烷。在使用所述聚有機矽氧烷的情況下，可通過液晶單元的構築後的光照射處理來提高液晶分子的配向限制力。聚合性不飽和基例如可列舉具有(甲基)丙烯醯基、乙烯基、苯乙烯基的基團等，但就對光的感度良好的觀點而言，其中優選為(甲基)丙烯醯基。所述聚有機矽氧烷可通過使例如所述式(C2-2)及式(C2-5)分別所表示的羧酸的至少1種、與含環氧基的聚有機矽氧烷進行反應而獲得。 As the polyorganosiloxane contained in the liquid crystal alignment agent of the present invention, a polyorganosiloxane having a polymerizable unsaturated group may be used. When the polyorganosiloxane is used, the alignment limiting force of the liquid crystal molecules can be improved by a light irradiation treatment after the liquid crystal cell is constructed. Examples of the polymerizable unsaturated group include a group having a (meth) acrylfluorenyl group, a vinyl group, and a styryl group. Among them, a (meth) acrylfluorenyl group is preferred from the viewpoint of good sensitivity to light. . The polyorganosiloxane can be reacted with, for example, at least one kind of a carboxylic acid represented by the formula (C2-2) and the formula (C2-5) with an epoxy-containing polyorganosiloxane And get.

[含環氧基的聚有機矽氧烷與羧酸的反應] [Reaction of epoxy-containing polyorganosiloxane with carboxylic acid]

含環氧基的聚有機矽氧烷、與具有液晶配向性基的羧酸(以下也稱為「羧酸(C)」)的反應優選為在催化劑以及有機溶劑的存在下進行。 Epoxy group-containing polyorganosiloxane and carboxylic acid ( The reaction (hereinafter also referred to as "carboxylic acid (C)") is preferably performed in the presence of a catalyst and an organic solvent.

與含環氧基的聚有機矽氧烷進行反應的羧酸可將羧酸 (C)單獨使用，或者與其他羧酸一起使用。例如出於使含環氧基的聚有機矽氧烷進行交聯的目的，可將作為其他羧酸的下述式(f)所表示的羧酸(F)與羧酸(C)同時使用。 Carboxylic acid reacted with epoxy-containing polyorganosiloxane (C) Use alone or with other carboxylic acids. For example, for the purpose of crosslinking an epoxy-group-containing polyorganosiloxane, a carboxylic acid (F) represented by the following formula (f), which is another carboxylic acid, may be used simultaneously with a carboxylic acid (C).

(式(f)中，R²³為碳數4~20的三級烴基。) (In formula (f), R ²³ is a tertiary hydrocarbon group having 4 to 20 carbon atoms.)

式(f)中的R²³優選為三級烷基或者具有環烷烴骨架的基團。R²³的具體例可列舉例如下述式(t-1)及式(t-2)分別所表示的基團等。 R ²³ in formula (f) is preferably a tertiary alkyl group or a group having a cycloalkane skeleton. Specific examples of R ²³ include groups represented by the following formula (t-1) and formula (t-2).

(式(t-1)中，R⁴¹、R⁴²及R⁴³分別獨立地為碳數1~4的烷基或者碳數4~20的脂環式烴基；式(t-2)中，R⁴⁴為碳數1~4 的烷基或者碳數4~20的1價脂環式烴基，M¹為與R⁴⁴所鍵結的碳原子一起形成碳數4~20的脂環式烴基的2價基；「*」表示鍵結於氧原子上的結合鍵。) (In formula (t-1), R ⁴¹ , R ⁴² and R ⁴³ are each independently an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 4 to 20 carbon atoms; in formula (t-2), R ⁴⁴ is an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and M ¹ is 2 to form an alicyclic hydrocarbon group having 4 to 20 carbon atoms together with a carbon atom bonded to R ⁴⁴ Valence group; "*" indicates a bonding bond to an oxygen atom.)

所述式(f)中的羧基的鍵結位置優選為對位。 The bonding position of the carboxyl group in the formula (f) is preferably a para position.

羧酸(F)的優選具體例可列舉例如下述式(f-1)及式(f-2)分別所表示的化合物等。羧酸(F)可單獨使用1種或者將2種以上組合使用。 Preferred specific examples of the carboxylic acid (F) include, for example, compounds represented by the following formula (f-1) and formula (f-2). The carboxylic acid (F) may be used alone or in combination of two or more.

相對於含環氧基的聚有機矽氧烷所具有的環氧基1莫耳，與含環氧基的聚有機矽氧烷進行反應的羧酸(總體量)的使用比例優選為設為0.001莫耳~10莫耳，更優選為設為0.01莫耳~5莫耳，尤其優選為設為0.05莫耳~2莫耳，特別優選為設為0.05莫耳~0.8莫耳。此外，通過使羧酸的使用比例少於含環氧基的聚有機矽氧烷所具有的環氧基，可獲得具有液晶配向性基及環氧基的聚有機矽氧烷。 1 mole of epoxy group compared to epoxy group-containing polyorganosiloxane Ear, the proportion of carboxylic acid (total amount) used to react with the epoxy-containing polyorganosiloxane is preferably set to 0.001 mol to 10 mol, more preferably set to 0.01 mol to 5 mol, It is particularly preferably set to 0.05 mol to 2 mol, and particularly preferably set to 0.05 mol to 0.8 mol. In addition, a polyorganosiloxane having a liquid crystal alignment group and an epoxy group can be obtained by making the use ratio of the carboxylic acid less than that of the epoxy group-containing polyorganosiloxane.

在合成具有聚合性不飽和基的聚有機矽氧烷的情況下，相對於含環氧基的聚有機矽氧烷所具有的環氧基1莫耳，所述式(C2-2)及式(C2-5)分別所表示的羧酸的使用比例(合計量)優選為設為0.001莫耳~5莫耳，更優選為設為0.01莫耳~1莫耳，尤其優選為設為0.03莫耳~0.6莫耳。 When synthesizing a polyorganosiloxane having a polymerizable unsaturated group Compared with the epoxy group containing 1 mole of epoxy group, The use ratio (total amount) of the carboxylic acid represented by the formula (C2-2) and the formula (C2-5) is preferably set to 0.001 mol to 5 mol, and more preferably set to 0.01 mol to 1 mol. The ear is particularly preferably 0.03 to 0.6 mole.

在使用所述羧酸(F)的情況下，其使用比例相對於環氧基1莫耳而設為0.01莫耳~1莫耳。更優選為0.02莫耳~0.3莫耳，尤其優選為0.04莫耳~0.2莫耳。 When the carboxylic acid (F) is used, its use ratio is relative to that of the ring Oxygen is 1 mole and 0.01 to 1 mole. It is more preferably 0.02 to 0.3 mol, and particularly preferably 0.04 to 0.2 mol.

反應中使用的催化劑例如可使用作為促進有機鹼、環氧化合物的反應的所謂硬化促進劑而公知的化合物等。此處，所述有機鹼例如可列舉：乙胺、哌嗪、哌啶等一級有機胺~二級有機胺；三乙胺、吡啶等三級有機胺；氫氧化四甲基銨等四級有機胺等。這些化合物中，有機鹼優選為三級有機胺或者四級有機胺。 The catalyst used in the reaction can be used, for example, as an organic base or epoxy Compounds known as so-called hardening accelerators for reaction of compounds. Here, the organic base includes, for example, primary organic amines to secondary organic amines such as ethylamine, piperazine, and piperidine; tertiary organic amines such as triethylamine and pyridine; and quaternary organic compounds such as tetramethylammonium hydroxide Amine, etc. Among these compounds, the organic base is preferably a tertiary organic amine or a quaternary organic amine.

另外，所述硬化促進劑例如可列舉：苄基二甲胺、2,4,6- 三(二甲基胺基甲基)苯酚等三級胺；2-甲基咪唑、2-正庚基咪唑等咪唑化合物；二苯基膦等有機磷化合物；苄基三苯基氯化鏻等四級鏻鹽；1,8-二氮雜雙環[5.4.0]十一烯-7或其有機酸鹽等二氮雜雙環烯烴；辛酸鋅、辛酸錫、鋁乙醯基丙酮錯合物等有機金屬化合物；溴化四乙基銨、溴化四-正丁基銨、氯化四乙基銨、氯化四-正丁基銨之類的四級銨鹽；三氟化硼、硼酸三苯酯之類的硼化合物；氯化鋅、氯化錫之類的金屬鹵素化合物等。這些化合物中，優選為四級銨鹽。 Examples of the hardening accelerator include benzyldimethylamine, 2,4,6- Tertiary amines such as tris (dimethylaminomethyl) phenol; imidazole compounds such as 2-methylimidazole and 2-n-heptylimidazole; organophosphorus compounds such as diphenylphosphine; benzyltriphenylphosphonium chloride, etc. Quaternary phosphonium salt; 1,8-diazabicyclo [5.4.0] undecene-7 or its organic acid salts, and other diazabicyclic olefins; zinc octoate, tin octoate, aluminum ethyl acetone complex, etc. Organometallic compounds; quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride; boron trifluoride, triborate Boron compounds such as phenyl esters; metal halogen compounds such as zinc chloride and tin chloride. Among these compounds, a quaternary ammonium salt is preferred.

相對於含環氧基的聚有機矽氧烷100重量份，所述催化劑以優選為100重量份以下、更優選為0.01重量份~100重量份、尤其優選為0.1重量份~20重量份的比例來使用。 With respect to 100 parts by weight of the epoxy-containing polyorganosiloxane, the catalyst The agent is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, It is particularly preferably used in a ratio of 0.1 to 20 parts by weight.

含環氧基的聚有機矽氧烷與羧酸的反應中可使用的有機溶劑例如可列舉：烴化合物、醚化合物、酯化合物、酮化合物、醯胺化合物、醇化合物等。這些化合物中，就原料及產物的溶解性以及產物的純化的容易度的觀點而言，優選為醚化合物、酯化合物、酮化合物，特別優選的溶劑的具體例可列舉：2-丁酮、2-己酮、甲基異丁基酮、環戊酮、環己酮以及乙酸丁酯等。另外，有機溶劑優選為以固體成分濃度(反應溶液中的溶劑以外的成分的合計重量在溶液的總重量中所占的比例)成為0.1重量%以上的比例來使用，更優選為以成為5重量%~50重量%的比例來使用。反應溫度優選為0℃~200℃，更優選為50℃~150℃。反應時間優選為0.1小時~50小時，更優選為0.5小時~20小時。 The reaction of epoxy-containing polyorganosiloxane with carboxylic acid is as follows: Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amidine compounds, and alcohol compounds. Among these compounds, ether compounds, ester compounds, and ketone compounds are preferred from the viewpoints of solubility of raw materials and products, and ease of product purification. Specific examples of particularly preferred solvents include 2-butanone, 2 -Hexanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and butyl acetate. The organic solvent is preferably used at a solid content concentration (a ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) of 0.1% by weight or more, and more preferably 5% by weight. % ~ 50% by weight. The reaction temperature is preferably 0 ° C to 200 ° C, and more preferably 50 ° C to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, and more preferably from 0.5 to 20 hours.

此外，所述含配向性基的聚有機矽氧烷的合成方法為通過含環氧基的聚有機矽氧烷所具有的環氧基的開環加成而導入液晶配向性基的方法。該合成方法簡便，而且是在可提高液晶配向性基的導入率的方面優選的方法。 In addition, a method for synthesizing the polyorganosiloxane containing an alignment group is as follows: A method for introducing a liquid crystal alignment group through ring-opening addition of an epoxy group in an epoxy-group-containing polyorganosiloxane. This synthesis method is simple and is a preferable method in terms of improving the introduction rate of the liquid crystal alignment group.

含配向性基的聚有機矽氧烷的利用凝膠滲透層析法來測定的聚苯乙烯換算的重量平均分子量優選為1,000~200,000，更優選為2,000~50,000，尤其優選為3,000~20,000。 Polyorganosiloxane containing alignment groups is obtained by gel permeation chromatography. The weight average molecular weight measured in terms of polystyrene is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 20,000.

≪化合物(D)≫ ≪Compound (D) ≫

所述化合物(D)是由下述式(1)所表示。 The compound (D) is represented by the following formula (1).

[化15] [Chemical 15]

所述式(1)中，就對光的反應性高的方面而言，A¹優選為選自由(甲基)丙烯醯基氧基、乙烯基及苯乙烯基所組成的組群中的至少一種，更優選為(甲基)丙烯醯基氧基。此外，(甲基)丙烯醯基氧基是包含丙烯醯基氧基以及甲基丙烯醯基氧基的含意。 In the formula (1), A ¹ is preferably at least one selected from the group consisting of a (meth) acrylfluorenyloxy group, a vinyl group, and a styryl group, in terms of high reactivity to light. One type is more preferably a (meth) acrylfluorenyloxy group. In addition, a (meth) acrylfluorenyloxy group means the meaning which includes acrylfluorenyloxy group and a methacrylfluorenyloxy group.

可與環氧基進行反應的官能基(A²)例如可列舉羧基、硫醇基、一級胺基、環氧基等。就與環氧基的反應性高的方面而言，其中優選為羧基。 Examples of the functional group (A ² ) capable of reacting with an epoxy group include a carboxyl group, a thiol group, a primary amine group, and an epoxy group. Among them, a carboxyl group is preferred because of its high reactivity with an epoxy group.

R¹的(m+n)價有機基例如可列舉：鏈狀烴基、脂環式烴基或者芳香族烴基等烴基，該烴基中的亞甲基經醚基、硫醚基、酯基或者硫酯基取代而成的基團等。R¹的碳數優選為1~30，更優選為3~20。 Examples of the (m + n) -valent organic group of R ¹ include a hydrocarbon group such as a chain hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. The methylene group in the hydrocarbon group is an ether group, a thioether group, an ester group, or a thioester. A group substituted with a group. The carbon number of R ¹ is preferably 1 to 30, and more preferably 3 to 20.

m優選為2~10，更優選為2~8。n優選為2~18，更優選為2~10，尤其優選為2~8。(m+n)優選為4~12，更優選為4~10。 m is preferably 2 to 10, and more preferably 2 to 8. n is preferably 2 to 18, more preferably 2 to 10, and particularly preferably 2 to 8. (m + n) is preferably 4 to 12, and more preferably 4 to 10.

所述式(1)所表示的化合物優選為下述式(1-1)所表示的化合物(以下也稱為「含羧酸的多元(甲基)丙烯酸酯」)。 The compound represented by the formula (1) is preferably a compound represented by the following formula (1-1) (hereinafter also referred to as a "carboxylic acid-containing polyvalent (meth) acrylate").

(式(1-1)中，R²為氫原子或者甲基；R¹、m及n與所述式(1)含意相同。) (In formula (1-1), R ² is a hydrogen atom or a methyl group; R ¹ , m, and n have the same meanings as in the formula (1).)

所述含羧酸的多元(甲基)丙烯酸酯的具體例可列舉例如下述式(1-1-1)~式(1-1-3)分別所表示的化合物等。 Specific examples of the carboxylic acid-containing poly (meth) acrylate include, for example, compounds represented by the following formulae (1-1-1) to (1-1-3).

(式(1-1-1)~式(1-1-3)中，R⁴為下述式(p-1)、式(p-2)或者式(p-3)所表示的基團；分子內的多個R⁴可相互相同，也可以不同；其中，多個R⁴中，至少1個為式(p-1)所表示的基團，且至少1個為式(p-2)所表示的基團以及式(p-3)所表示的基團的至少任一者；j為1~10的整數。) (In formulae (1-1-1) to (1-1-3), R ⁴ is a group represented by the following formula (p-1), formula (p-2), or formula (p-3) ; Multiple R ^{4 in the} molecule may be the same as or different from each other; among them, at least one of the plurality of R ⁴ is a group represented by formula (p-1), and at least one is a formula (p-2 At least one of the group represented by) and the group represented by formula (p-3); j is an integer from 1 to 10.)

(式(p-1)~式(p-3)中，R²為氫原子或者甲基，R³⁰為碳數1~6的烷二基或者伸苯基。) (In the formulae (p-1) to (p-3), R ² is a hydrogen atom or a methyl group, and R ³⁰ is an alkanediyl group or a phenyl group having 1 to 6 carbon atoms.)

所述式(1-1-1)~式(1-1-3)中，所述式(p-1)所表示的基團的數量(x)、與所述式(p-2)所表示的基團以及所述式(p-3)所表示的基團的數量(合計數y)的比例可根據所使用的聚合物或添加劑的種類及調配量等來適當調整。在橫向電場方式的液晶顯示元件的情況下，就減少殘像的方面而言，另外，在垂直配向型的液晶顯示元件的情況下，就加快液晶分子的響應速度的方面而言，優選為x多於y。 In the formulae (1-1-1) to (1-1-3), the number (x) of groups represented by the formula (p-1) and the number of groups represented by the formula (p-2) The proportion of the groups represented and the number (total number y) of the groups represented by the formula (p-3) can be appropriately adjusted depending on the type of the polymer or additive used, the blending amount, and the like. In the case of a liquid crystal display element of the lateral electric field type, in terms of reducing afterimages, and in the case of a vertical alignment type liquid crystal display element, in terms of accelerating the response speed of liquid crystal molecules, it is preferably x. More than y.

所述化合物(D)可使用市售品，或者也可以使用通過合成而獲得的化合物。化合物(D)的市售品例如可列舉東亞合成(股)製造的商品名「TO-2349」、「TO-1382」等。 As the compound (D), a commercially available product may be used, or a compound obtained by synthesis may be used. Examples of commercially available products of the compound (D) include trade names "TO-2349" and "TO-1382" manufactured by Toa Kosei Co., Ltd.

另外，在合成所述化合物(D)的情況下，其合成方法並無特別限定，可將有機化學的常法適當組合來進行。若列舉所述式(1-1)所表示的含羧酸的多元(甲基)丙烯酸酯為一例來進行說明，則可利用例如以下方法來合成：[1]使具有羥基的多官能(甲基)丙烯酸酯化合物、與丁二酸酐等酸酐進行反應的方法(與下述流程(I)相對應)；[2]使多官能(甲基)丙烯酸酯化合物與具有硫醇基的羧酸進行反應(邁克爾加成(Michael addition))的方法(與下述流程(II)相對應)等。 In the case of synthesizing the compound (D), the method for synthesizing the compound (D) is not particularly limited, and an ordinary method of organic chemistry can be appropriately combined and carried out. If listed The carboxylic acid-containing poly (meth) acrylate represented by the formula (1-1) is described as an example, and can be synthesized by, for example, the following method: [1] Making a polyfunctional (meth) acrylic acid having a hydroxyl group Method for reacting an ester compound with an acid anhydride such as succinic anhydride (corresponding to the following scheme (I)); [2] reacting a polyfunctional (meth) acrylate compound with a carboxylic acid having a thiol group (Michael Method (corresponding to the following flow (II)) and the like.

(式中，R¹、R²、m及n與所述式(1-1)含意相同；R³⁰為碳數1~6的烷二基或者伸苯基。) (In the formula, R ¹ , R ² , m, and n have the same meanings as in the formula (1-1); R ³⁰ is an alkyldiyl group or a phenylene group having 1 to 6 carbon atoms.)

相對於液晶配向劑中的聚合物成分的總體100重量份，所述化合物(D)的調配比例優選為設為1重量份~30重量份。通過設為1重量份以上，能夠充分獲得液晶配向性或配向穩定性的改善效果。另外，通過設為30重量份以下，能夠抑制液晶配向不良。更優選為3重量份~25重量份的範圍，尤其優選為5重量份~20重量份的範圍。此外，所述化合物(D)可單獨使用1種或者將2種以上組合使用。 The compounding ratio of the compound (D) is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the entire polymer component in the liquid crystal alignment agent. By setting it to 1 part by weight or more, the effect of improving liquid crystal alignment or alignment stability can be sufficiently obtained. In addition, by setting it to 30 parts by weight or less, liquid crystal alignment defects can be suppressed. A range of 3 to 25 parts by weight is more preferred, and a range of 5 to 20 parts by weight is particularly preferred. Moreover, the said compound (D) can be used individually by 1 type Alternatively, two or more of them may be used in combination.

≪其他成分≫ ≪Other ingredients≫

本發明的液晶配向劑可視需要而含有其他成分。所述其他成分的優選具體例可列舉：例如分子內具有2個以上環氧基的化合物且不相當於所述化合物(D)的化合物(以下也稱為「含環氧基的化合物」)、分子內具有2個以上羧基的化合物且不相當於所述化合物(D)的化合物(以下也稱為「多元羧酸」)等。 The liquid crystal aligning agent of this invention may contain other components as needed. Preferable specific examples of the other components include, for example, a compound having two or more epoxy groups in the molecule and not corresponding to the compound (D) (hereinafter also referred to as "epoxy-containing compound"), A compound having two or more carboxyl groups in the molecule and not corresponding to the compound (D) (hereinafter also referred to as "polycarboxylic acid") and the like.

<含環氧基的化合物> <Epoxy-containing compound>

含環氧基的化合物可出於提高液晶配向膜的與基板表面的黏接性的目的而使用。含環氧基的化合物的具體例可列舉例如：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、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、1,3,5,6-四縮水甘油基-2,4-己二醇、N,N,N',N'-四縮水甘油基-對苯二胺、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基醚、N,N,N',N'-四縮水甘油基-2,2'-二甲基-4,4'-二胺基聯苯、三羥甲基丙烷三縮水甘油醚、N,N,N',N'-四縮水甘油基-間二甲苯二胺、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-苄基胺、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、N,N,N',N'-四縮水甘油基-1,4-二胺基環己烷、雙(N,N-二縮水甘油基-4-胺基環己基)甲烷、1,4-雙(N,N-二縮水甘油基胺基甲基)環己烷、1,4-雙(N,N-二縮水甘油基胺基甲基)苯、1,3,5-三(N,N-二縮水甘油基胺基甲基)環己烷、下述式(e-1)~式(e-3) The epoxy group-containing compound can be used for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate surface. Specific examples of the epoxy group-containing compound include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and diglyceride. Glycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-p-phenylenediamine, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenyl ether, N, N, N', N'-tetraglycidyl-2,2'-dimethyl- 4,4'-diaminobiphenyl, trimethylolpropane triglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl -Benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, N, N, N ', N'-tetraglycidyl -1,4-diaminocyclohexane, bis (N, N-diglycidyl-4-aminocyclohexyl) methane, 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,4-bis (N, N-diglycidylaminomethyl) benzene, 1,3,5-tris (N, N -Diglycidylaminomethyl) cyclohexane, the following formulae (e-1) to (e-3)

分別所表示的化合物等。除此以外，還可使用國際公開第2009/096598號中記載的含環氧基的聚有機矽氧烷。 Respective compounds and the like. In addition, an epoxy-group-containing polyorganosiloxane described in International Publication No. 2009/096598 can also be used.

在將含環氧基的化合物添加於液晶配向劑中的情況下，相對於液晶配向劑中所含的聚合物的合計100重量份，所述含環氧基的化合物的調配比率優選為40重量份以下，更優選為0.1重量份~30重量份。 When an epoxy group-containing compound is added to a liquid crystal alignment agent Below, the compounding ratio of the epoxy group-containing compound is preferably 40 parts by weight or less, and more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total of the polymers contained in the liquid crystal alignment agent.

<多元羧酸> <Polycarboxylic acid>

多元羧酸可出於提高液晶配向膜的液晶配向性的目的而使用。多元羧酸的具體例可列舉例如：反丁烯二酸、丙二酸、己二酸、對苯二甲酸、間苯二甲酸、癸二酸、二苯基醚-4,4'-二羧酸、吡啶-2,6-二羧酸等二羧酸；1,2,4-丁烷三羧酸、1,2,3-環己烷三羧酸、偏苯三甲酸、1,2,4-萘三羧酸等三羧酸；1,2,3,4-環丁烷四羧酸、2,3,5-三羧基環戊基乙酸、環戊烷四羧酸、環己烷四羧酸、均苯四甲酸等四羧酸等。 The polycarboxylic acid can be used for the purpose of improving the liquid crystal alignment property of the liquid crystal alignment film. Specific examples of the polycarboxylic acid include fumaric acid, malonic acid, adipic acid, terephthalic acid, isophthalic acid, sebacic acid, and diphenyl ether-4,4'-dicarboxylic acid. Acid, dicarboxylic acid such as pyridine-2,6-dicarboxylic acid; 1,2,4-butanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, trimellitic acid, 1,2, Tricarboxylic acids such as 4-naphthalenetricarboxylic acid; 1,2,3,4-cyclobutanetetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid, cyclopentanetetracarboxylic acid, cyclohexane tetra Tetracarboxylic acids such as carboxylic acid and pyromellitic acid.

在將多元羧酸添加於液晶配向劑中的情況下，相對於液晶配向劑中所含的聚合物的合計100重量份，所述多元羧酸的調配比率優選為40重量份以下，更優選為0.1重量份~30重量份。 When a polycarboxylic acid is added to a liquid crystal alignment agent, The total amount of the polymer contained in the crystal alignment agent is 100 parts by weight, and the blending ratio of the polycarboxylic acid is preferably 40 parts by weight or less, and more preferably 0.1 to 30 parts by weight.

所述其他成分除了所述以外，例如可列舉：官能性矽烷化合物、分子內具有1個環氧基的化合物、分子內具有至少1個氧雜環丁基的化合物、雙順丁烯二醯亞胺化合物、抗氧化劑、光增感劑等。這些其他成分的調配量可在不損及本發明效果的範圍內適當調整。 Examples of the other components other than the above include functional silanes. A compound, a compound having one epoxy group in the molecule, a compound having at least one oxetanyl group in the molecule, a biscis butylene diimide compound, an antioxidant, a photosensitizer, and the like. The blending amount of these other components can be appropriately adjusted within a range that does not impair the effect of the present invention.

本發明的液晶配向劑的優選形態可列舉：(I)僅包含選自由聚醯胺酸、聚醯胺酸酯以及聚醯亞胺所組成的組群中的一種作為聚合物成分的形態；(II)包含選自由聚醯胺酸、聚醯胺酸酯以及聚醯亞胺所組成的組群中的一種、與聚有機矽氧烷作為聚合物成分的形態；(III)僅包含聚有機矽氧烷作為聚合物成分的形態等。 Preferred embodiments of the liquid crystal alignment agent of the present invention include: (I) a mode including only one selected from the group consisting of polyamidic acid, polyamidate, and polyimide as a polymer component; II) a form containing a polyamine compound selected from the group consisting of polyamidic acid, polyamidate, and polyimide, and polyorganosiloxane as a polymer component; (III) containing polyorganosiloxane only The form of oxane as a polymer component and the like.

這些形態中，優選為所述(II)的形態，所述(II)的形態中更優選為聚有機矽氧烷為含環氧基的聚有機矽氧烷。相對於聚醯胺酸、聚醯胺酸酯以及聚醯亞胺的合計100重量份，所述(II)的形態中的聚有機矽氧烷的調配比例優選為設為1重量份~30重量份，更優選為設為5重量份~20重量份。 Among these forms, the form of (II) is preferred, and the form of (II) is more preferably a polyorganosiloxane containing an epoxy group-containing polyorganosiloxane. The blending ratio of the polyorganosiloxane in the form of (II) is preferably 1 to 30 parts by weight based on 100 parts by weight of the total of polyamic acid, polyamidate, and polyimide. The amount is more preferably 5 to 20 parts by weight.

此外，在將聚合性成分導入配向膜中且在構築液晶單元後使用對液晶單元進行光照射的技術來製造液晶顯示元件的情況下，優選為調配側鏈上具有聚合性不飽和基的聚合物作為液晶配向劑的聚合物成分的至少一部分。側鏈上具有聚合性不飽和基的聚合物優選為選自由聚醯胺酸、聚醯胺酸酯、聚醯亞胺及聚有機矽氧烷所組成的組群中的至少一種，更優選為聚有機矽氧烷。特別是在所述(II)的形態中，通過將聚有機矽氧烷設為具有聚合性不飽和基的聚合物，可以少的光照射量來獲得液晶配向性的改善效果，因此優選。 In addition, when a polymerizable component is introduced into an alignment film and a liquid crystal display element is manufactured using a technique of irradiating the liquid crystal cell with light after the liquid crystal cell is constructed, a polymer having a polymerizable unsaturated group on a side chain is preferably prepared. At least a part of a polymer component as a liquid crystal alignment agent. Polymerizable unsaturated group The polymer is preferably at least one selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyorganosiloxane, and more preferably polyorganosiloxane. Especially in the aspect (II), it is preferable to use a polyorganosiloxane as a polymer having a polymerizable unsaturated group to obtain a liquid crystal alignment improvement effect with a small amount of light irradiation.

≪溶劑≫ ≪Solvent≫

本發明的液晶配向劑是將聚合物成分、化合物(D)以及視需要而任意調配的其他成分優選為溶解於有機溶劑中來構成。 The liquid crystal alignment agent of the present invention is preferably configured by dissolving a polymer component, a compound (D), and other components optionally blended in an organic solvent.

此處，用於製備本發明的液晶配向劑的溶劑例如可列舉：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、二異丁基酮、丙酸異戊酯、異丁酸異戊酯、二異戊基醚、碳酸伸乙酯、碳酸伸丙酯等。這些溶劑可單獨使用或者將2種以上混合使用。 Here, the solvent used to prepare the liquid crystal alignment agent of the present invention may be listed, for example. Examples: N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy- 4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol Diethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol 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, diisobutyl Ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate and the like. These solvents can be used alone or in combination of two or more.

本發明的液晶配向劑中的固體成分濃度(液晶配向劑的溶劑以外的成分的合計重量在液晶配向劑的總重量中所占的比例)是考慮到黏性、揮發性等來適當選擇，但優選為1重量%~10重量%的範圍。即，本發明的液晶配向劑是通過以後述方式塗布於基板表面，優選為進行加熱，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，在固體成分濃度小於1重量%的情況下，該塗膜的膜厚變得過小而無法獲得良好的液晶配向膜。另一方面，在固體成分濃度超過10重量%的情況下，塗膜的膜厚變得過大而無法獲得良好的液晶配向膜，另外，液晶配向劑的黏性增大而塗布特性劣化。 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 to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, and the like, but is preferably in a range of 1% to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to a method described later The substrate surface is preferably heated to form a coating film as a liquid crystal alignment film or a coating film as 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 becomes too small. However, a good liquid crystal alignment film cannot be obtained. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, and a good liquid crystal alignment film cannot be obtained. In addition, the viscosity of the liquid crystal alignment agent increases and the coating characteristics deteriorate.

特別優選的固體成分濃度的範圍根據在基板上塗布液晶配向劑時所使用的方法而不同。例如在利用旋轉器法的情況下，固體成分濃度特別優選為1.5重量%~4.5重量%的範圍。在利用印刷法的情況下，特別優選為將固體成分濃度設為3重量%~9重量%的範圍，由此將溶液黏度設為12mPa．s~50mPa．s的範圍。在利用噴墨法的情況下，特別優選為將固體成分濃度設為1重量%~5重量%的範圍，由此將溶液黏度設為3mPa．s~15mPa．s的範圍。製備液晶配向劑時的溫度優選為10℃~50℃，更優選為20℃~30℃。 A particularly preferable range of the solid content concentration depends on the coating liquid on the substrate. The method used for the crystal alignment agent varies. For example, when a spinner method is used, the solid content concentration is particularly preferably in a range of 1.5% to 4.5% by weight. In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3% to 9% by weight, and thereby set the solution viscosity to 12 mPa. s ~ 50mPa. The range of s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1% to 5% by weight, and thereby set the solution viscosity to 3 mPa. s ~ 15mPa. The range of s. The temperature when preparing the liquid crystal alignment agent is preferably 10 ° C to 50 ° C, and more preferably 20 ° C to 30 ° C.

≪液晶配向膜以及液晶顯示元件≫ ≪Liquid crystal alignment film and liquid crystal display element≫

本發明的液晶配向膜是利用以所述方式製備的液晶配向劑來形成。另外，本發明的液晶顯示元件具備使用該液晶配向劑而形成的液晶配向膜。應用本發明的液晶顯示元件的工作模式並無特別限定，可應用於TN型、STN型、IPS型、FFS型、VA型、MVA型等多種工作模式。本發明的液晶顯示元件可利用例如包括以下的步驟(1)~步驟(3)的方法來製造。 The liquid crystal alignment film of the present invention is formed using the liquid crystal alignment agent prepared in the manner described above. The liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The working mode of the liquid crystal display element to which the present invention is applied is not particularly limited, and it can be applied to various working modes such as TN type, STN type, IPS type, FFS type, VA type, and MVA type. The liquid crystal display element of the present invention can be manufactured by a method including the following steps (1) to (3), for example.

[步驟(1)：塗膜的形成] [Step (1): Formation of Coating Film]

首先，在一對基板的各表面塗布液晶配向劑，繼而對其進行加熱而形成塗膜。 First, a liquid crystal alignment agent is applied to each surface of a pair of substrates, and then they are heated to form a coating film.

(1-1)在製造TN型、STN型、VA型或者MVA型的液晶顯示元件的情況下，將設置有經圖案化的透明導電膜的兩塊基板作為一對，在各基板的透明性導電膜的形成面上，優選為利用膠版印刷法、旋塗法、輥式塗布機法或者噴墨印刷法來分別塗布本發明的液晶配向劑。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(脂環式烯烴)等塑膠的透明基板。設置於基板的一面的透明導電膜使用包含氧化錫(SnO₂)的奈塞(NESA)膜(美國PPG公司注冊商標)、包含氧化銦-氧化錫(In₂O₃-SnO₂)的氧化銦錫(indium tin oxide，ITO)膜等。為了獲得經圖案化的透明導電膜，例如可利用以下方法：形成無圖案的透明導電膜後，通過光蝕刻來形成圖案的方法；形成透明導電膜時使用具有所需圖案的遮罩的方法等。塗布液晶配向劑時，為了使基板表面以及透明導電膜與塗膜的黏接性更良好，也可以對基板表面中形成塗膜的面，實施預先塗布官能性矽烷化合物、官能性鈦化合物等的前處理。 (1-1) When manufacturing a TN type, STN type, VA type, or MVA type liquid crystal display element, two substrates provided with a patterned transparent conductive film are used as a pair, and the transparency of each substrate is It is preferable that the liquid crystal alignment agent of this invention is apply | coated on the formation surface of a conductive film by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method, respectively. Here, the substrate can be, for example, glass such as float glass, soda glass, or polyethylene terephthalate, polybutylene terephthalate, polyether, polycarbonate, or poly (alicyclic olefin). ) And other plastic transparent substrates. As the transparent conductive film provided on one side of the substrate, a Nesa film (registered trademark of the United States PPG Corporation) containing tin oxide (SnO ₂ ) and indium oxide containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Indium tin oxide (ITO) film and the like. In order to obtain a patterned transparent conductive film, for example, the following methods can be used: a method of forming a pattern by forming a transparent conductive film without a pattern, and then forming a pattern by photoetching; a method of forming a transparent conductive film using a mask having a desired pattern, and the like . When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the surface on which the coating film is formed may be coated with a functional silane compound, a functional titanium compound, or the like in advance. Before processing.

(1-2)在製造IPS型或者FFS型液晶顯示元件的情況下，通過在設置有包含經圖案化為梳齒型的透明導電膜或者金屬膜的電極的基板的電極形成面、與未設置電極的對向基板的一面上，分別塗布本發明的液晶配向劑，繼而對各塗布面進行加熱來形成塗膜。關於此時所使用的基板的材質、透明導電膜的材質、塗布方法、塗布後的加熱條件、透明導電膜或者金屬膜的圖案化方法、基板的前處理、以及所形成的塗膜的優選膜厚，與所述(1-1)相同。金屬膜例如可使用包含鉻等金屬的膜。 (1-2) In the case of manufacturing an IPS-type or FFS-type liquid crystal display element, an electrode forming surface of a substrate including an electrode including a transparent conductive film or a metal film patterned in a comb-tooth shape is provided, and The side of the electrode facing the substrate Then, the liquid crystal alignment agent of the present invention is applied separately, and then each application surface is heated to form a coating film. About the material of the substrate used at this time, the material of the transparent conductive film, the coating method, the heating conditions after coating, the method of patterning the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film of the formed coating film The thickness is the same as that of (1-1). As the metal film, for example, a film containing a metal such as chromium can be used.

在所述(1-1)及(1-2)的任一種情況下，均通過在基板上塗布液晶配向劑後，將有機溶劑去除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。優選為通過加熱處理來去除溶劑。具體而言，在塗布液晶配向劑後，出於防止所塗布的配向劑的流掛等目的，優選為實施預加熱(預烘烤)。預烘烤溫度優選為30℃~200℃，更優選為40℃~150℃，特別優選為40℃~100℃。預烘烤時間優選為0.25分鐘~10分鐘，更優選為0.5分鐘~5分鐘。然後，出於將溶劑完全去除的目的，另外，出於將視需要而存在於聚合物中的醯胺酸結構進行熱醯亞胺化的目的，而實施煅燒(後烘烤)步驟。此時的煅燒溫度(後烘烤溫度)優選為80℃~300℃，更優選為120℃~250℃。後烘烤時間優選為5分鐘~200分鐘，更優選為10分鐘~100分鐘。以所述方式形成的膜的膜厚優選為0.001μm~1μm，更優選為0.005μm~0.5μm。 In any of the cases (1-1) and (1-2), After the liquid crystal alignment agent is applied on the plate, the organic solvent is removed to form a coating film as a liquid crystal alignment film or a coating film as a liquid crystal alignment film. The solvent is preferably removed by heat treatment. Specifically, after applying the liquid crystal alignment agent, it is preferable to perform preheating (prebaking) for the purpose of preventing the applied alignment agent from sagging or the like. The pre-baking temperature is preferably 30 ° C to 200 ° C, more preferably 40 ° C to 150 ° C, and particularly preferably 40 ° C to 100 ° C. The pre-baking time is preferably 0.25 minutes to 10 minutes, and more preferably 0.5 minutes to 5 minutes. Then, a calcination (post-baking) step is performed for the purpose of completely removing the solvent, and for the purpose of thermally arsonizing the arsenic acid structure that is present in the polymer as necessary. 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 5 minutes to 200 minutes, and more preferably 10 minutes to 100 minutes. The film thickness of the film formed in this manner is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

此外，在本發明的液晶配向劑中所含有的聚合物為聚醯胺酸，或為聚醯胺酸酯，或者為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下，也可以通過在塗膜形成後進一步進行加熱來進行脫水閉環反應，製成進一步醯亞胺化的塗膜。 The polymer contained in the liquid crystal alignment agent of the present invention is polyfluorene. In the case of an amino acid, which is either a polyfluorene ester or a fluorinated polymer having a fluorinated imine ring structure and a fluorinated acid structure, dehydration ring closure may be performed by further heating after the formation of a coating film. The reaction results in a coating film that is further imidized.

[配向能力賦予處理] [Alignment ability granting process]

在製造TN型、STN型、IPS型或者FFS型的液晶顯示元件的情況下，通常進行對所述步驟(1)中形成的塗膜賦予液晶配向能力的處理。由此，對塗膜賦予液晶分子的配向能力而成為液晶配向膜。賦予配向能力的處理可列舉摩擦處理或利用光配向法的處理等，所述摩擦處理是利用捲繞有包含例如尼龍、人造絲、棉等纖維的布的輥，將塗膜向一定方向摩擦。其中，就可抑制因灰塵或靜電而引起的顯示不良的產生或良率的下降的方面、以及可對塗膜均勻地賦予液晶配向能力的方面而言，優選為使用光配向法。另一方面，在製造VA型液晶顯示元件的情況下，雖可將所述步驟(1)中形成的塗膜直接用作液晶配向膜，但也可以對該塗膜實施所述處理。 When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal display element, a process of providing a liquid crystal alignment ability to the coating film formed in the step (1) is generally performed. Thereby, the alignment ability of liquid crystal molecules is given to a coating film, and it becomes a liquid crystal alignment film. Examples of the treatment for imparting the alignment ability include a rubbing treatment or a treatment using a photo-alignment method. The rubbing treatment is a method in which a coating film is rubbed in a certain direction by a roll wound with a cloth containing fibers such as nylon, rayon, and cotton. Among them, a photo-alignment method is preferably used in terms of suppressing the occurrence of display failure or a decrease in yield due to dust or static electricity, and for uniformly imparting liquid crystal alignment ability to a coating film. On the other hand, in the case of manufacturing a VA-type liquid crystal display element, although the coating film formed in the step (1) may be directly used as a liquid crystal alignment film, the coating film may be subjected to the treatment described above.

此外，也可以對摩擦處理後的液晶配向膜進一步進行以下處理：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；或者在液晶配向膜表面的一部分形成抗蝕劑膜後，向與剛才的摩擦處理不同的方向進行摩擦處理，然後後將抗蝕劑膜去除的處理；從而使液晶配向膜在每個區域具有不同的液晶配向能力。該情況下，能夠改善所得液晶顯示元件的視野特性。 In addition, the liquid crystal alignment film after the rubbing treatment may be further performed. Down treatment: a process of changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays; or after forming a resist film on a part of the surface of the liquid crystal alignment film, the surface is different from the previous rubbing treatment. The rubbing treatment is performed in the direction, and then the resist film is removed, so that the liquid crystal alignment film has different liquid crystal alignment capabilities in each region. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved.

光配向法中，通過對形成於基板上的塗膜，照射偏光或者非偏光的放射線，來對塗膜賦予液晶配向能力。放射線例如可使用包含150nm~800nm波長的光的紫外線以及可見光線。在放射線為偏光的情況下，可以是直線偏光，也可以是部分偏光。另外，在所使用的放射線為直線偏光或者部分偏光的情況下，可自垂直的方向對基板面進行照射，也可以自傾斜方向進行照射，或者也可以將這些照射加以組合來進行。在照射非偏光的放射線的情況下，照射的方向設為傾斜方向。 In the photo-alignment method, a coating film formed on a substrate is irradiated with polarized light or In order to provide the liquid crystal alignment ability to the coating film by using non-polarized radiation. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. Put When the rays are polarized light, linearly polarized light or partially polarized light may be used. In addition, when the radiation used is linearly polarized or partially polarized, the substrate surface may be irradiated from a vertical direction, or may be irradiated from an oblique direction, or a combination of these irradiations may be performed. In the case where non-polarized radiation is irradiated, the direction of irradiation is set to an oblique direction.

所使用的光源例如可使用：低壓水銀燈、高壓水銀燈、氘燈、金屬鹵化物燈、氬共振燈、氙燈、準分子雷射等。優選的波長區域的紫外線可通過將光源與例如濾光器、繞射光柵等併用的方法等來獲得。 The light source used may be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, Deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser, etc. Ultraviolet rays in a preferred wavelength region can be obtained by a method in which a light source is used in combination with, for example, a filter, a diffraction grating, and the like.

光照射可利用以下方法來進行：對後烘烤步驟後的塗膜進行照射的方法；對預烘烤步驟後且後烘烤步驟前的塗膜進行照射的方法；在預烘烤步驟以及後烘烤步驟的至少任一者中，在塗膜的加熱時對塗膜進行照射的方法等。光的照射量優選為100J/m²~50,000J/m²，更優選為300J/m²~20,000J/m²。另外，為了提高反應性，可一邊對塗膜進行加溫一邊對塗膜進行光照射。加溫時的溫度通常為30℃~250℃，優選為40℃~200℃，更優選為50℃~150℃。通過這種光照射處理而在基板上形成液晶配向膜。 Light irradiation can be performed by the following methods: a method of irradiating the coating film after the post-baking step; a method of irradiating the coating film after the pre-baking step and before the post-baking step; during the pre-baking step and after In at least one of the baking steps, a method of irradiating the coating film during heating of the coating film, and the like. Light irradiation amount is preferably ^{100J / m 2 ~ 50,000J / m} 2, and more preferably ^{300J / m 2 ~ 20,000J / m} 2. In order to improve the reactivity, the coating film may be irradiated with light while the coating film is being heated. The temperature during heating is usually 30 ° C to 250 ° C, preferably 40 ° C to 200 ° C, and more preferably 50 ° C to 150 ° C. A liquid crystal alignment film is formed on the substrate by such a light irradiation process.

[步驟(2)：單元的構築] [Step (2): Construction of Unit]

(2-1)通過準備以所述方式形成有液晶配向膜的2塊(一對)基板，來製造以液晶配向膜對向的方式經由液晶配置有該一對基板的液晶單元。製造液晶單元時，例如可列舉以下的2種方法。首先，第一方法為以往已知的方法。該方法中，首先以各液晶配向膜對向的方式，經由間隙(單元間隙)而將2塊基板對向配置，使用密封劑將2塊基板的周邊部貼合，在由基板表面以及密封劑劃分的單元間隙內注入填充液晶後，將注入孔密封，由此製造液晶單元。另外，第二方法是稱為液晶滴注(One Drop Fill，ODF)方式的方法。該方法中，在形成有液晶配向膜的2塊基板中的其中一塊基板上的既定部位，塗布例如紫外光硬化性的密封材，進而在液晶配向膜面上的既定的數個部位滴加液晶後，以液晶配向膜對向的方式貼合另一塊基板。並且，將液晶在基板的整個面上鋪開，繼而對基板的整個面照射紫外光，使密封劑硬化，由此製造液晶單元。在利用任一種方法的情況下，均理想的是通過對以所述方式製造的液晶單元，進而加熱至所使用的液晶成為各向同性相的溫度後，緩緩冷卻至室溫，從而去除液晶填充時的流動配向。密封劑例如可使用含有硬化劑以及作為間隔物的氧化鋁球的環氧樹脂等。液晶層的厚度優選為設為1μm~5μm。 (2-1) By preparing two (pair) substrates on which the liquid crystal alignment film is formed as described above, a liquid crystal cell in which the pair of substrates are arranged via the liquid crystal in a manner in which the liquid crystal alignment films face each other is manufactured. When manufacturing a liquid crystal cell, the following two methods are mentioned, for example. First, the first method is a conventionally known method. In this method, first In the method of facing the film, two substrates are arranged to face each other through a gap (cell gap), and the peripheral portions of the two substrates are bonded using a sealant, and the liquid crystal is injected and filled in the cell gap divided by the substrate surface and the sealant. Then, the injection hole was sealed, thereby manufacturing a liquid crystal cell. The second method is a method called a liquid crystal drip (ODF) method. In this method, a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed is coated with, for example, a UV-curable sealing material, and then liquid crystals are added dropwise to predetermined positions on the liquid crystal alignment film surface. Then, another substrate is bonded in a manner that the liquid crystal alignment film faces each other. Then, the liquid crystal is spread on the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, thereby manufacturing a liquid crystal cell. In the case of using any method, it is desirable to remove the liquid crystal by slowly cooling the liquid crystal cell manufactured as described above to a temperature at which the used liquid crystal becomes an isotropic phase, and then slowly cooling to room temperature. Flow alignment during filling. As the sealant, for example, an epoxy resin containing a hardener and alumina balls as a spacer can be used. The thickness of the liquid crystal layer is preferably 1 μm to 5 μm.

(2-2)在製造PSA方式的液晶顯示元件的情況下，除了將光聚合性化合物與液晶一起注入或者滴加的方面以外，以與所述(2-1)相同的方式構築液晶單元。 (2-2) In the case of manufacturing a PSA-type liquid crystal display element, A liquid crystal cell was constructed in the same manner as in (2-1) above except that the photopolymerizable compound was injected or dropped together with the liquid crystal.

[步驟(3)：對液晶單元的光照射] [Step (3): Light Irradiation on Liquid Crystal Cell]

液晶單元的構築後，對於液晶單元，自其外側進行光照射。通過該光照射來記憶液晶分子的傾倒方向，由此可實現液晶配向的穩定化。在縱向電場方式的液晶顯示元件中，以對一對基板所具有的導電膜間施加電壓的狀態來對液晶單元進行光照射，在橫向電場方式的液晶顯示元件中，以不對導電膜間施加電壓的狀態來對液晶單元進行光照射。此處施加的電壓例如可設為5V~50V的直流或者交流。另外，所照射的光例如可使用包含150nm~800nm波長的光的紫外線以及可見光線，但優選為包含300nm~400nm波長的光的紫外線。照射光的光源例如可使用：低壓水銀燈、高壓水銀燈、氘燈、金屬鹵化物燈、氬共振燈、氙燈、準分子雷射等。此外，所述的優選波長區域的紫外線可通過將光源與例如濾光器、繞射光柵等併用的手段等而獲得。光的照射量優選為1,000J/m²以上且小於200,000J/m²，更優選為1,000J/m²~100,000J/m²。 After the liquid crystal cell is constructed, the liquid crystal cell is irradiated with light from its outside. By this light irradiation, the tilting direction of the liquid crystal molecules is memorized, whereby the liquid crystal alignment can be stabilized. In the liquid crystal display element of the vertical electric field type, the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of a pair of substrates. In the liquid crystal display element of the horizontal electric field type, no voltage is applied between the conductive films. To irradiate the liquid crystal cell with light. The voltage applied here can be, for example, 5V to 50V DC or AC. In addition, as the light to be irradiated, for example, ultraviolet rays including visible light with a wavelength of 150 nm to 800 nm and visible rays may be used, but ultraviolet rays including light having a wavelength of 300 to 400 nm are preferred. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and the like can be used. In addition, the ultraviolet rays in the above-mentioned preferred wavelength region can be obtained by means such as a combination of a light source and a filter, a diffraction grating, or the like. The irradiation amount of light is preferably 1,000 J / m ² or more and less than 200,000 J / m ² , and more preferably 1,000 J / m ² to 100,000 J / m ² .

接著，可通過在液晶單元的外側表面貼合偏光板來獲得本發明的液晶顯示元件。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」的偏光膜而成的偏光板，該「H膜」是一邊使聚乙烯醇延伸配向一邊使其吸收碘而成的膜；或者包含H膜其本身的偏光板。此外，在對塗膜進行摩擦處理的情況下，2塊基板是以各塗膜中的摩擦方向相互形成既定的角度，例如正交或者反平行的方式對向配置。 Next, it can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell. The liquid crystal display element of the present invention. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include a polarizing plate in which a polarizing film called an "H film" is sandwiched by a protective film of cellulose acetate, and the "H film" extends polyvinyl alcohol while A film formed by aligning one side to absorb iodine; or a polarizing plate including the H film itself. In addition, when the coating film is subjected to a rubbing treatment, the two substrates are arranged facing each other such that the rubbing directions in the respective coating films form a predetermined angle with each other, for example, orthogonal or anti-parallel.

本發明的液晶顯示元件可有效地應用於多種裝置，例如可用於：鐘錶、便攜型遊戲機、文字處理器、筆記型個人電腦、汽車導航系統、攝錄機、個人數位助理(Personal Digital Assistant，PDA)、數碼照相機、手機、智慧手機、各種監視器、液晶電視、資訊顯示器等的各種顯示表示裝置。 The liquid crystal display element of the present invention can be effectively applied to a variety of devices, such as: clocks, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, and personal digital assistants (Personal Digital Assistant, PDA), digital cameras, mobile phones, smartphones, various monitors, LCD TVs, information displays and other display devices.

[實施例] [Example]

以下，利用實施例來對本發明進一步進行具體說明，但本發明並不限定於這些實施例。 Hereinafter, the present invention will be further specifically described using examples, but the present invention is not limited to these examples.

利用以下方法來測定合成例中的各聚合物溶液的溶液黏度、聚醯亞胺的醯亞胺化率、聚合物的重量平均分子量以及環氧當量。 The following methods were used to measure the solution viscosity of each polymer solution in the synthesis example, the fluorene imidization rate of the polyfluorene, the weight average molecular weight of the polymer, and the epoxy equivalent.

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

對於使用既定的溶劑而將聚合物濃度製備為10重量%的溶液，使用E型旋轉黏度計，在25℃下測定聚合物溶液的溶液黏度[mPa．s]。 For a solution having a polymer concentration of 10% by weight using a given solvent, an E-type rotary viscometer was used to measure the solution viscosity of the polymer solution at 25 ° C [mPa. s].

[聚醯亞胺的醯亞胺化率] [Perylene imidation rate of polyimide]

將聚醯亞胺的溶液投入至純水中，將所得的沉澱在室溫下充分地減壓乾燥後，溶解於氘化二甲基亞碸中，以四甲基矽烷作為基準物質，在室溫測定¹H-核磁共振(¹H-Nuclear magnetic resonance，¹H-NMR)。根據所得的¹H-NMR光譜，使用下述數式(1)所表示的式子來求出醯亞胺化率[%]。 The solution of polyfluoreneimide was poured into pure water, and the obtained precipitate was dried under reduced pressure at room temperature, and then dissolved in deuterated dimethylsulfine, and measured at room temperature using tetramethylsilane as a reference substance. ¹ H- NMR ^{(1 H-Nuclear magnetic resonance,} 1 H-NMR). Based on the obtained ¹ H-NMR spectrum, the fluorene imidization ratio [%] was determined using the formula represented by the following formula (1).

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

(數式(1)中，^A1是在化學位移10ppm附近出現的源自NH基的質子的峰值面積，A²是源自其他質子的峰值面積，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 formula (1), ^A 1 is a peak area of NH-derived protons occurring near a chemical shift of 10 ppm, A ² is a peak area of other protons, and α is a precursor of other protons relative to the polymer. (Polyamic acid) Proportion of the number of one proton of the NH group.)

[聚合物的重量平均分子量] [Polymer average molecular weight]

聚合物的重量平均分子量Mw是利用以下條件的凝膠滲透層析法來測定的聚苯乙烯換算值。 The weight average molecular weight Mw of the polymer is a polystyrene conversion value measured by gel permeation chromatography under the following conditions.

管柱：東曹(Tosoh)(股)製造，TSKgelGRCXLII Column: Made by Tosoh, TSKgelGRCXLII

溶劑：四氫呋喃 Solvent: Tetrahydrofuran

溫度：40℃ Temperature: 40 ° C

壓力：68kgf/cm² Pressure: 68kgf / cm ²

[環氧當量] [Epoxy equivalent]

環氧當量是依據日本工業標準(Japanese Industrial Standards，JIS)C2105的「鹽酸-甲基乙基酮法」來測定的值。 The epoxy equivalent is a value measured according to the "hydrochloric acid-methyl ethyl ketone method" of Japanese Industrial Standards (JIS) C2105.

以下的合成例視需要通過以下述合成規模來重複進行，來確保以下的合成例、實施例以及比較例中使用的所需量的產物。 The following synthesis examples are repeated as necessary on the following synthesis scale to ensure the required amount of products used in the following synthesis examples, examples, and comparative examples.

<化合物(D)的合成> <Synthesis of Compound (D)> [合成例1：化合物(1-2-1)的合成] [Synthesis Example 1: Synthesis of Compound (1-2-1)]

依據下述流程1來合成化合物(1-2-1)。 Compound (1-2-1) was synthesized according to the following scheme 1.

[化21] [Chemical 21]

在具備溫度計、回流管以及滴加漏斗的100mL三口燒瓶中，添加化合物(1-2A)6.24g、乙腈8.64g、2,6-二-第三丁基-4-甲氧基苯酚6mg以及巰基丙酸2.40g，加熱至50℃。繼而，花1小時滴加三乙胺6.07g後，在50℃下使其直接進行1小時反應。反應結束後，添加乙酸乙酯100mL，以1M乙二酸水100mL進行1次、以水進行5次分液洗滌，然後以丁基溶纖劑進行2次溶劑置換，由此獲得固體成分濃度為20%的化合物(1-2-1)的丁基溶纖劑溶液40g。 In a 100 mL three-necked flask equipped with a thermometer, a reflux tube, and a dropping funnel, 6.24 g of compound (1-2A), 8.64 g of acetonitrile, 6 mg of 2,6-di-tert-butyl-4-methoxyphenol, and mercapto group were added. 2.40 g of propionic acid, heated to 50 ° C. Then, 6.07 g of triethylamine was added dropwise over 1 hour, and the reaction was directly performed at 50 ° C for 1 hour. After the reaction was completed, 100 mL of ethyl acetate was added, and the solution was washed once with 100 mL of 1M oxalic acid water and 5 times with liquid separation, and then the solvent was replaced twice with butyl cellosolve to obtain a solid content concentration of 20%. 40 g of a butyl cellosolve solution of the compound (1-2-1).

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

依據下述流程2來合成化合物(1-3-1)。 Compound (1-3-1) was synthesized according to the following scheme 2.

[化22] [Chemical 22]

在具備溫度計、回流管以及滴加漏斗的100mL三口燒瓶中，添加化合物(1-3A)12.2g、乙腈15.8g、2,6-二-第三丁基-4-甲氧基苯酚12mg以及巰基丙酸3.61g，加熱至50℃。繼而，花1小時滴加三乙胺6.07g後，在50℃下使其直接進行1小時反應。反應結束後，添加乙酸乙酯100mL，以1M乙二酸水100mL進行1次、以水進行5次分液洗滌，然後，以丁基溶纖劑進行2次溶劑置換，由此獲得固體成分濃度為20%的化合物(1-3-1)的丁基溶纖劑溶液70g。 In a 100 mL three-necked flask equipped with a thermometer, a reflux tube, and a dropping funnel, 12.2 g of compound (1-3A), 15.8 g of acetonitrile, 12 mg of 2,6-di-third-butyl-4-methoxyphenol, and mercapto group were added. 3.61 g of propionic acid was heated to 50 ° C. Then, 6.07 g of triethylamine was added dropwise over 1 hour, and the reaction was directly performed at 50 ° C for 1 hour. After the reaction was completed, 100 mL of ethyl acetate was added, and the solution was washed once with 100 mL of 1M oxalic acid water and 5 times with water. Then, the solvent was replaced twice with butyl cellosolve to obtain a solid content concentration of 20 70 g of a butyl cellosolve solution of the compound (1-3-1).

<聚有機矽氧烷的合成> <Synthesis of Polyorganosiloxane>

[合成例3：含環氧基的聚有機矽氧烷(EPS-1)的合成] [Synthesis Example 3: Synthesis of Epoxy-Containing Polyorganosiloxane (EPS-1)]

在具備攪拌機、溫度計、滴加漏斗以及回流冷卻管的反應容器中，投入2-(3,4-環氧基環己基)乙基三甲氧基矽烷100.0g、甲基異丁基酮500g以及三乙胺10.0g，在室溫下混合。繼而，自滴加漏斗中花30分鐘滴加去離子水100g後，在回流下一邊混合一邊在80℃下進行6小時反應。反應結束後，取出有機層，利用0.2重量%硝酸銨水溶液來進行洗滌，直至洗滌後的水成為中性為止，然後在減壓下蒸餾去除溶劑以及水，由此以黏稠的透明液體的形式獲得聚有機矽氧烷(EPS-1)。 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone, and three 10.0 g of ethylamine was mixed at room temperature. Then, 100 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and then the reaction was performed at 80 ° C. for 6 hours while mixing under reflux. After the reaction, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a thick transparent liquid. Polyorganosiloxane (EPS-1).

對該聚有機矽氧烷(EPS-1)進行¹H-NMR分析，結果在化學位移(δ)=3.2ppm附近，如理論強度般獲得基於氧雜環丙基的峰值，確認反應中未產生環氧基的副反應。聚有機矽氧烷(EPS-1)的Mw為2,200，環氧當量為186g/莫耳。 The polyorganosiloxane (EPS-1) was subjected to ¹ H-NMR analysis. As a result, a peak based on an oxetanyl group was obtained at a chemical shift (δ) = 3.2 ppm as a theoretical intensity, and it was confirmed that no peak was generated during the reaction. Epoxy side reactions. Polyorganosiloxane (EPS-1) had a Mw of 2,200 and an epoxy equivalent of 186 g / mole.

[合成例4：含環氧基的聚有機矽氧烷(EPS-2)的合成] [Synthesis Example 4: Synthesis of Epoxy-Containing Polyorganosiloxane (EPS-2)]

在具備攪拌機、溫度計、滴加漏斗以及回流冷卻管的反應容器中，投入2-(3,4-環氧基環己基)乙基三甲氧基矽烷458.7g、3-甲基丙烯醯氧基丙基三甲氧基矽烷162.8g、甲基異丁基酮3108g以及三乙胺62.2g，在室溫下混合。繼而，自滴加漏斗中花30分鐘滴加去離子水621.5g後，一邊在回流下混合，一邊在80℃下進行6小時反應。反應結束後，取出有機層，利用0.2重量%硝酸銨水溶液來進行洗滌，直至洗滌後的水成為中性為止，然後在減壓下蒸餾去除溶劑以及水，由此以黏稠的透明液體的形式獲得聚有機矽氧烷(EPS-2)。該聚有機矽氧烷(EPS-2)的重量平均分子量 Mw為2,900。 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 458.7 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-methacryloxypropane were charged. 162.8 g of trimethoxysilane, 3108 g of methyl isobutyl ketone, and 62.2 g of triethylamine were mixed at room temperature. Then, 621.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was performed at 80 ° C. for 6 hours while mixing under reflux. After the reaction, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a thick transparent liquid. Polyorganosiloxane (EPS-2). Weight average molecular weight of the polyorganosiloxane (EPS-2) Mw is 2,900.

[合成例5：含液晶配向性基的羧酸(3-6-1)的合成] [Synthesis Example 5: Synthesis of carboxylic acid (3-6-1) containing liquid crystal alignment group]

依據下述流程3來合成羧酸(3-6-1)。 The carboxylic acid (3-6-1) was synthesized according to the following scheme 3.

．化合物(3-6-1A)的合成． Synthesis of compound (3-6-1A)

在具備氮氣導入管、回流管的2L茄型燒瓶中，投入對羥基苯甲醛24.4g(0.2mol)、碳酸鉀138.2g(1.0mol)、以及丙酮600mL(MS乾燥)後，添加4-溴丁腈32.6g(0.22mol)來進行3小時回流。反應結束後，添加乙酸乙酯1L，以水1L進行洗滌後，以飽和碳酸鈉水溶液200mL洗滌2次，進而以水300mL洗滌3次。接著，以硫酸鎂使有機層乾燥後，在減壓下蒸餾去除溶劑，由此獲得化合物(3-6-1A)的黃色透明液體35.5g。 24.4 g (0.2 mol) of p-hydroxybenzaldehyde, 138.2 g (1.0 mol) of potassium carbonate, and 600 mL of acetone (MS dried) were added to a 2 L eggplant type flask equipped with a nitrogen introduction tube and a reflux tube, and then 4-bromobutane was added. 32.6 g (0.22 mol) of nitrile was refluxed for 3 hours. After completion of the reaction, 1 L of ethyl acetate was added, and the mixture was washed with 1 L of water, and then washed twice with 200 mL of a saturated sodium carbonate aqueous solution, and then washed three times with 300 mL of water. Next, after the organic layer was dried with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 35.5 g of a yellow transparent liquid of the compound (3-6-1A).

．化合物(3-6-1)的合成． Synthesis of compound (3-6-1)

在具備回流管、溫度計及氮氣導入管的1000mL三口燒瓶中，將化合物(3-6-1)35.52g(0.188mol)、吡啶224mL以及丙二酸39.13g(0.376mol)溶解。接著，添加哌啶16.0g(0.188mol)，進行3小時回流。反應結束後，添加乙酸乙酯800mL、四氫呋喃(tetrahydrofuran，THF)800mL，以2N的鹽酸水1L洗滌1次，以1N鹽酸水洗滌2次，然後添加飽和碳酸鈉水1.5L，以乙酸乙酯400mL洗滌2次。接著，添加乙酸乙酯400mL、THF 800mL，利用8N鹽酸水500mL而成為酸性後，以水400mL洗滌3次，以硫酸鎂進行乾燥後，進行濃縮、結晶化(crystallization)，由此獲得羧酸(3-6-1)的白色結晶25.2g。 In a 1000 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, 35.52 g (0.188 mol) of compound (3-6-1), 224 mL of pyridine, and 39.13 g (0.376 mol) of malonic acid were dissolved. Next, 16.0 g (0.188 mol) of piperidine was added, Perform reflux for 3 hours. After the reaction was completed, 800 mL of ethyl acetate and 800 mL of tetrahydrofuran (THF) were added, washed once with 1 L of 2 N hydrochloric acid water, and washed twice with 1 N hydrochloric acid water, and then 1.5 L of saturated sodium carbonate water was added, and 400 mL of ethyl acetate was added. Wash twice. Next, 400 mL of ethyl acetate and 800 mL of THF were added, and the mixture was made acidic with 500 mL of 8N hydrochloric acid water, washed three times with 400 mL of water, dried with magnesium sulfate, and then concentrated and crystallized to obtain a carboxylic acid ( 3-6-1) 25.2 g of white crystals.

[合成例6：含液晶配向性基的羧酸(3-9-1)的合成] [Synthesis Example 6: Synthesis of carboxylic acid (3-9-1) containing liquid crystal alignment group]

在具備冷卻管的500mL的三口燒瓶中，投入4-溴二苯基醚20g、乙酸鈀0.18g、三(2-甲苯基)膦0.98g、三乙胺32.4g以及二甲基乙醯胺135mL，進行混合而製成溶液。接著，使用注射器，將丙烯酸7g添加於所述溶液中，進行攪拌，然後在120℃下一邊攪拌一邊進行3小時反應。利用薄層層析法(Thin Layer Chromatography，TLC)來確認反應的結束後，將反應溶液冷卻至室溫。將不溶物過濾分離後，將濾液注入至1N鹽酸300mL中，回收析出物。將該析出物在包含乙酸乙酯及己烷的混合溶劑(乙酸乙酯：己烷=1：1(容積比))中進行再結晶，由此獲得下述式(3-9-1)所表示的化合物(羧酸(3-9-1))8.4g。 In a 500 mL three-necked flask equipped with a cooling tube, 20 g of 4-bromodiphenyl ether, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine, and 135 mL of dimethylacetamide were charged. , And mix to make a solution. Next, 7 g of acrylic acid was added to the solution using a syringe, and the mixture was stirred, and then reacted for 3 hours while stirring at 120 ° C. After confirming the completion of the reaction by Thin Layer Chromatography (TLC), the reaction solution was cooled to room temperature. After the insoluble matter was separated by filtration, the filtrate was poured into 300 mL of 1N hydrochloric acid, and the precipitate was recovered. This precipitate was recrystallized in a mixed solvent (ethyl acetate: hexane = 1: 1 (volume ratio)) containing ethyl acetate and hexane, thereby obtaining a compound of the following formula (3-9-1). 8.4 g of the compound (carboxylic acid (3-9-1)).

[合成例6-1：羧酸(F-2)的合成] [Synthesis Example 6-1: Synthesis of carboxylic acid (F-2)]

依據下述流程來合成羧酸(F-2)。 The carboxylic acid (F-2) was synthesized according to the following scheme.

．化合物(F-2D)的合成． Synthesis of compound (F-2D)

在具備回流管及氮氣導入管的200mL茄型燒瓶中，添加對苯二甲酸單甲酯21.6g、亞硫醯氯88mL以及N,N-二甲基甲醯胺5滴，在80℃下進行1小時回流。反應結束後，利用抽吸機將亞硫醯氯減壓蒸餾去除，由此獲得化合物(F-2B)的淡黃色固體。對該固體添加四氫呋喃50mL而製成A液。另一方面，在具備溫度計、氮氣導入管以及滴加漏斗的500mL的三口燒瓶中，添加1-乙基環戊醇13.7g，進行冰浴冷卻。繼而，花30分鐘滴加1.6M正丁基鋰己烷溶液90mL。接著，花30分鐘滴加A液後，直接在冰浴冷卻下進行攪拌，2小時後添加水100mL來停止反應。接著，添加乙酸乙酯400mL，以水400mL洗滌4次，進行濃縮脫水，由此獲得化合物(F-2D)的橙色液體32.8g。 In a 200 mL eggplant-type flask equipped with a reflux tube and a nitrogen introduction tube, 21.6 g of monomethyl terephthalate, 88 mL of thionyl chloride, and 5 drops of N, N-dimethylformamide were added, and the reaction was performed at 80 ° C. Reflux for 1 hour. After completion of the reaction, thionyl chloride was distilled off under reduced pressure using a suction machine, whereby a pale yellow solid of the compound (F-2B) was obtained. To this solid, 50 mL of tetrahydrofuran was added to prepare liquid A. On the other hand, 13.7 g of 1-ethylcyclopentanol was added to a 500 mL three-necked flask equipped with a thermometer, a nitrogen introduction tube, and a dropping funnel, and the mixture was cooled in an ice bath. Then, 90 mL of a 1.6 M n-butyllithium hexane solution was added dropwise over 30 minutes. Next, after the A solution was added dropwise over 30 minutes, the solution was directly stirred under ice-cooling. After 2 hours, 100 mL of water was added to stop the reaction. then, 400 mL of ethyl acetate was added and washed 4 times with 400 mL of water, and concentrated and dehydrated to obtain 32.8 g of an orange liquid of compound (F-2D).

．化合物(F-2)的合成． Synthesis of compound (F-2)

在1L茄型燒瓶中，投入化合物(F-2D)32.8g、甲醇150mL、水50mL以及氫氧化鋰一水合物9.95g，在室溫進行1小時反應。反應結束後，添加四氫呋喃250mL以及乙酸乙酯300mL，以稀鹽酸400mL洗滌一次，以水300mL洗滌3次。以硫酸鎂進行乾燥後，加以濃縮，將添加己烷而析出的結晶過濾、乾燥，由此獲得化合物(F-2)的黃色針狀結晶14.1g。 In a 1L eggplant-type flask, 32.8 g of compound (F-2D), 150 mL of methanol, 50 mL of water, and 9.95 g of lithium hydroxide monohydrate were charged, and a reaction was performed at room temperature for 1 hour. After the reaction was completed, 250 mL of tetrahydrofuran and 300 mL of ethyl acetate were added, washed once with 400 mL of dilute hydrochloric acid, and washed three times with 300 mL of water. After drying with magnesium sulfate, it was concentrated, and crystals precipitated by adding hexane were filtered and dried to obtain 14.1 g of yellow needle-like crystals of the compound (F-2).

[合成例7：含配向性基的聚有機矽氧烷(S-2-1)的合成] [Synthesis Example 7: Synthesis of polyorganosiloxane (S-2-1) containing an alignment group]

在100mL的三口燒瓶中，投入所述合成例3中合成的聚有機矽氧烷(EPS-1)3.5g、甲基異丁基酮24g、羧酸(3-6-1)2.42g(相對於聚有機矽氧烷(EPS-1)所具有的矽原子，相當於50莫耳%)以及商品名「UCAT 18X」(三亞普羅(San-Apro)(股)製造，環氧化合物的硬化促進劑)0.35g，進行5小時回流。反應結束後，在反應混合物中添加甲醇，生成沉澱，對將該沉澱物溶解於乙酸乙酯中而獲得的溶液進行3次水洗後，蒸餾去除溶劑，由此獲得聚有機矽氧烷(S-2-1)的白色粉末5g。聚有機矽氧烷(S-2-1)的重量平均分子量為9,200。 In a 100 mL three-necked flask, 3.5 g of the polyorganosiloxane (EPS-1) synthesized in Synthesis Example 3, 24 g of methyl isobutyl ketone, and 2.42 g of carboxylic acid (3-6-1) (relative) Made of polyorganosiloxane (EPS-1) with silicon atoms equivalent to 50 mol% and trade name "UCAT 18X" (San-Apro), which promotes hardening of epoxy compounds Agent) 0.35 g, and refluxed for 5 hours. After the reaction was completed, methanol was added to the reaction mixture to generate a precipitate. The solution obtained by dissolving the precipitate in ethyl acetate was washed three times with water, and then the solvent was distilled off to obtain a polyorganosiloxane (S- 5g of white powder 2-1). The polyorganosiloxane (S-2-1) had a weight average molecular weight of 9,200.

[合成例8~合成例10、合成例10A：含配向性基的聚有機矽氧烷的合成] [Synthesis Example 8 to Synthesis Example 10, Synthesis Example 10A: Synthesis of polyorganosiloxane containing an alignment group]

除了將所使用的化合物的種類及量設為如下述表1所述以外，利用與所述合成例7相同的方法來合成含配向性基的聚有機矽氧烷(S-2-2)~聚有機矽氧烷(S-2-4)、聚有機矽氧烷(S-2-10)。 A polyorganosiloxane (S-2-2) containing an alignment group was synthesized by the same method as in Synthesis Example 7 except that the types and amounts of the compounds used were as described in Table 1 below. Polyorganosiloxane (S-2-4), Polyorganosiloxane (S-2-10).

表1中，羧酸的調配量的數值表示相對於含環氧基的聚有機矽氧烷所具有的矽原子而言的投入量[莫耳%]。 In Table 1, the numerical value of the compounding quantity of a carboxylic acid shows the input amount [mol%] with respect to the silicon atom which the polyorganosiloxane containing an epoxy group has.

[合成例11：聚醯胺酸(PA-1)的合成] [Synthesis Example 11: Synthesis of Polyamidic Acid (PA-1)]

將2,3,5-三羧基環戊基乙酸二酐5.55g、及下述式(3-7DA)所表示的二胺化合物9.45g溶解於N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone，NMP)85g中，在室溫下進行6小時反應。將反應混合物注入至大量過剩的甲醇中，使反應產物沉澱。將該沉澱物以甲醇洗滌，在減壓下以40℃進行15小時乾燥，由此獲得聚醯胺酸(PA-1)10g。 5.55 g of 2,3,5-tricarboxycyclopentylacetic dianhydride and 9.45 g of a diamine compound represented by the following formula (3-7DA) were dissolved in N-methyl-2-pyrrolidone (N-methyl- 2-pyrrolidone (NMP) (85 g) was reacted at room temperature for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate a reaction product. This precipitate was washed with methanol, and dried at 40 ° C. for 15 hours under reduced pressure to obtain 10 g of polyamic acid (PA-1).

[合成例12：聚醯胺酸(PA-2)的合成] [Synthesis Example 12: Synthesis of Polyamine (PA-2)]

將環丁烷四羧酸二酐19.61g(0.1莫耳)、及4,4'-二胺基-2,2'- 二甲基聯苯21.23g(0.1莫耳)溶解於N-甲基-2-吡咯烷酮367.6g中，在室溫下進行6小時反應。將反應混合物注入至大量過剩的甲醇中，使反應產物沉澱。將該沉澱物以甲醇洗滌，在減壓下以40℃進行15小時乾燥，由此獲得聚醯胺酸(PA-2)35g。 Cyclobutane tetracarboxylic dianhydride 19.61 g (0.1 mole) and 4,4'-diamino-2,2'- 21.23 g (0.1 mole) of dimethylbiphenyl was dissolved in 367.6 g of N-methyl-2-pyrrolidone, and the reaction was performed at room temperature for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate a reaction product. This precipitate was washed with methanol, and dried at 40 ° C. for 15 hours under reduced pressure, thereby obtaining 35 g of polyamidic acid (PA-2).

[實施例1] [Example 1] (1)液晶配向劑的製備 (1) Preparation of liquid crystal alignment agent

將作為聚合物成分的含配向性基的聚有機矽氧烷(S-2-1)100重量份及聚醯胺酸(PA-2)1,000重量份、作為化合物(D)的東亞合成(股)製造的「TO-1382」100重量份、作為其他成分的偏苯三甲酸200重量份進行混合，向其中添加作為溶劑的N-甲基-2-吡咯烷酮(NMP)以及丁基溶纖劑(Butyl Cellosolve，BC)，製成溶劑組成為NMP：BC=50：50(重量比)、固體成分濃度為3.0重量%的溶液。利用孔徑為0.2μm的過濾器將該溶液進行過濾，由此製備液晶配向劑(A-1)。 100 parts by weight of an oriented polyorganosiloxane (S-2-1) and 1,000 parts by weight of a polyamic acid (PA-2) as a polymer component, and a compound (D) of East Asia Synthetic Co., Ltd. 100 parts by weight of "TO-1382" manufactured by the company, and 200 parts by weight of trimellitic acid as other components were mixed, and N-methyl-2-pyrrolidone (NMP) and a butyl cellosolve (Butyl Cellosolve) as solvents were added thereto. , BC), a solution having a solvent composition of NMP: BC = 50: 50 (weight ratio) and a solid content concentration of 3.0% by weight was prepared. This solution was filtered through a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (A-1).

(2)橫向電場方式液晶顯示元件的製造 (2) Manufacturing of a liquid crystal display element using a lateral electric field method

將在其中一面具有經圖案化為梳齒狀的包含鉻的2系統金屬電極的玻璃基板、與未設置電極的對向玻璃基板作為一對，在玻璃基板的具有電極的面與對向玻璃基板的一面上，使用旋轉器來塗布所述製備的液晶配向劑(A-1)，利用80℃的加熱板進行1分鐘預烘烤後，在將庫內進行了氮氣置換的烘箱中，以200℃加熱(後烘烤)1小時而形成膜厚為0.1μm的塗膜。將表示玻璃基板上的電極圖案構成的概略圖示於圖1中。以下，將該橫向電場方式液晶顯示元件所具有的2系統的金屬電極(導電膜圖案)分別稱為電極11以及電極12。 A glass substrate having a two-system metal electrode including chromium patterned in a comb-tooth shape on one side and a counter glass substrate without an electrode as a pair, and a surface having an electrode on the glass substrate and a counter glass substrate On one side, the prepared liquid crystal alignment agent (A-1) was applied using a spinner, and pre-baking was performed on a heating plate at 80 ° C. for one minute. Heating (post-baking) at 1 ° C for 1 hour to form a coating film having a film thickness of 0.1 µm. A schematic diagram showing a configuration of an electrode pattern on a glass substrate is shown in FIG. 1. Hereinafter, this lateral electric field type liquid The two-system metal electrodes (conductive film patterns) of a crystal display element are referred to as an electrode 11 and an electrode 12, respectively.

繼而，對這些塗膜表面，分別使用Hg-Xe燈以及格蘭泰勒棱鏡(Glan-Taylor prism)，自基板法線方向照射包含313nm的明線的偏光紫外線300J/m²而獲得具有液晶配向膜的一對基板。在所述基板中的其中一塊的具有液晶配向膜的面上散佈珠粒間隔物，進而，通過絲網印刷，在外周塗布加入有直徑為5.5μm的氧化鋁球的環氧樹脂黏接劑。然後，使一對基板的各基板中的液晶配向膜面對向，以照射偏光紫外線時的各基板的朝向成為相反的方式重疊而壓接，在150℃下花1小時使黏接劑進行熱硬化。 Then, on the surfaces of these coating films, Hg-Xe lamps and Glan-Taylor prisms were respectively used to irradiate polarized ultraviolet light 300 J / m ² including bright lines of 313 nm from the direction of the substrate normal to obtain a liquid crystal alignment film. Of a pair of substrates. Bead spacers were spread on the surface of one of the substrates having a liquid crystal alignment film, and further, an epoxy resin adhesive with alumina balls having a diameter of 5.5 μm was coated on the periphery by screen printing. Then, the liquid crystal alignment films of each of the pair of substrates were faced, and the orientations of the substrates were reversed when polarized ultraviolet rays were irradiated, and the pressure-bonding was performed, and the adhesive was heated at 150 ° C for 1 hour to heat the adhesive. hardening.

繼而，自液晶注入口向基板間的間隙中，填充在默克(Merck)公司製造的液晶「MLC-7028」中添加有0.3wt%下述式(L-1)所表示的聚合性液晶而成的液晶混合物，然後，利用環氧系黏接劑將液晶注入口加以密封。然後，為了去除液晶注入時的流動配向，而在150℃下對其進行加熱後緩緩冷卻至室溫，進而自液晶單元的外側實施UV光照射(照射量：2,000mJ/cm²(λ=365nm))。接著，在基板的外側兩面，以偏光板的偏光方向相互正交，且與液晶配向膜的偏光紫外線的光軸的對基板面的射影方向正交的方式貼合所述偏光板，由此製造液晶顯示元件。 Next, a gap between the liquid crystal injection port and the substrate was filled with a liquid crystal "MLC-7028" manufactured by Merck and 0.3 wt% of a polymerizable liquid crystal represented by the following formula (L-1) was added. The resulting liquid crystal mixture is then sealed with a liquid crystal injection port using an epoxy-based adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C. and gradually cooled to room temperature, and then UV light was irradiated from the outside of the liquid crystal cell (irradiation amount: 2,000 mJ / cm ² (λ = 365nm)). Next, the polarizing plates are laminated on both outer surfaces of the substrate so that the polarization directions of the polarizing plates are orthogonal to each other and orthogonal to the projection direction of the optical axis of the polarized ultraviolet rays of the liquid crystal alignment film on the substrate surface, thereby manufacturing the polarizing plates. Liquid crystal display element.

[化27] [Chemical 27]

(3)液晶配向性的評價 (3) Evaluation of liquid crystal alignment

對於所述製造的液晶顯示元件，利用光學顯微鏡來觀察當接通．斷開(ON．OFF)(施加．解除)5V電壓時的明暗變化中的異常區域的有無。此時，將完全未觀察到異常區域的情況評價為液晶配向性「優」，將觀察到少量異常區域的情況評價為液晶配向性「良」，將觀察到多處異常區域的情況評價為液晶配向性「不良」。其結果為，實施例1中為液晶配向性「良」。 For the manufactured liquid crystal display element, use an optical microscope to observe when it is turned on. ON (OFF) (apply. Release) the presence or absence of an abnormal region during a change in light and shade when the voltage is 5V. At this time, the case where no abnormal region was observed at all was evaluated as "excellent" in liquid crystal alignment, the case where a small number of abnormal regions was observed was "good" in liquid crystal alignment, and the case where multiple abnormal regions were observed was evaluated as liquid crystal. Orientation is "bad". As a result, the liquid crystal alignment was "good" in Example 1.

(4)殘像特性的評價 (4) Evaluation of afterimage characteristics

將所述製造的橫向電場方式液晶顯示元件放置於25℃、1氣壓的環境下，對電極12不施加電壓，且對電極11施加交流電壓3.5V與直流電壓5V的合成電壓2小時。然後即刻對電極11以及電極12的兩者施加交流4V的電壓。測定自對兩電極開始施加交流4V的電壓的時刻起，直至以目視無法確認到電極11及電極12的光透過性之差為止的時間。在該時間為20秒以上且小於60秒的情況下評價為殘像特性「優」，在60秒以上且小於100秒的情況下評價為殘像特性「良」，在100秒以上且小於150秒的情況下評價為殘像特性「可」，在超過150秒的情況下評價為殘像特性「不良」。其結果為，實施例1中為殘像特性「良」。 The manufactured lateral electric field type liquid crystal display element was placed in an environment of 25 ° C. and 1 atmosphere, no voltage was applied to the electrode 12, and a combined voltage of an AC voltage of 3.5 V and a DC voltage of 5 V was applied to the electrode 2 for 2 hours. Then, a voltage of 4V AC was immediately applied to both the electrode 11 and the electrode 12. The time from the moment when the voltage of 4V AC was applied to both electrodes was measured until the difference of the light transmittance of the electrode 11 and the electrode 12 could not be confirmed visually. When this time is 20 seconds or more and less than 60 seconds, it is evaluated as an afterimage characteristic "excellent", and when it is 60 seconds or more and less than 100 seconds, it is evaluated as an afterimage characteristic "good", and it is 100 seconds or more and less than 150 In the case of seconds, the after-image characteristic was evaluated as “OK”, and in the case of more than 150 seconds, the after-image characteristic was evaluated as “Defective”. As a result, the afterimage characteristic was "good" in Example 1.

[實施例2~實施例20、比較例1、比較例2] [Example 2 to Example 20, Comparative Example 1, Comparative Example 2]

除了將所使用的聚合物、化合物(D)以及其他成分的種類及量變更為如下述表2所述以外，進行與實施例1相同的操作，由此製備液晶配向劑(A-2)~液晶配向劑(A-20)、液晶配向劑(R-1)、液晶配向劑(R-2)。另外，使用所得的液晶配向劑(A-2)~液晶配向劑(A-20)、液晶配向劑(R-1)、液晶配向劑(R-2)，以與實施例1相同的方式製造液晶顯示元件，並且進行液晶配向性以及殘像特性的評價。將其結果示於下述表3中。 A liquid crystal alignment agent (A-2) was prepared by performing the same operation as in Example 1 except that the types and amounts of the polymer, compound (D), and other components used were changed as described in Table 2 below. Liquid crystal alignment agent (A-20), liquid crystal alignment agent (R-1), and liquid crystal alignment agent (R-2). In addition, using the obtained liquid crystal alignment agent (A-2) to liquid crystal alignment agent (A-20), liquid crystal alignment agent (R-1), and liquid crystal alignment agent (R-2), it was manufactured in the same manner as in Example 1. A liquid crystal display element was evaluated for liquid crystal alignment and afterimage characteristics. The results are shown in Table 3 below.

表2中，括弧內的數值表示各化合物的調配比例(重量份)。化合物(D)的含羧酸的多元丙烯酸酯(商品名「TO-1382」以及「TO-2349」)是由東亞合成(股)來獲取。表2中的化合物(D)以及其他成分的略稱分別為以下含意。 In Table 2, the numerical value in parentheses shows the compounding ratio (weight part) of each compound. The carboxylic acid-containing polyacrylate (trade names "TO-1382" and "TO-2349") of the compound (D) was obtained from Toa Synthetic Co., Ltd. The abbreviations of the compound (D) and other components in Table 2 have the following meanings.

(化合物(D)) (Compound (D))

D-1：所述式(1-2-1)所表示的化合物 D-1: Compound represented by the formula (1-2-1)

D-2：所述式(1-3-1)所表示的化合物 D-2: the compound represented by the formula (1-3-1)

(其他添加劑) (Other additives)

EP-1：N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷 EP-1: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

如表3所示，實施例1~實施例20的液晶顯示元件均為液晶配向性以及殘像特性為「優」或者「良」的評價。與此相對，液晶配向劑中不含化合物(D)的比較例1、比較例2中，液晶配向性為「不良」的評價，殘像特性為「可」的評價。 As shown in Table 3, all the liquid crystal display elements of Examples 1 to 20 were evaluated as having "good" or "good" liquid crystal alignment and afterimage characteristics. In contrast, in Comparative Example 1 and Comparative Example 2 in which the compound (D) was not included in the liquid crystal alignment agent, the liquid crystal alignment Evaluation of "bad" property and evaluation of "possible" afterimage characteristics.

[合成例13：含液晶配向性基的羧酸(7-3-1)的合成] [Synthesis Example 13: Synthesis of carboxylic acid (7-3-1) containing liquid crystal alignment group]

依據下述流程4來合成羧酸(7-3-1)。 The carboxylic acid (7-3-1) was synthesized according to the following scheme 4.

．化合物(7-3-1A)的合成． Synthesis of compound (7-3-1A)

在具備滴加漏斗、溫度計及氮氣導入管的1L的三口燒瓶中，添加羥基苯甲酸5.00g(36.22mmol)、四氫呋喃150mL、第三丁醇100mL以及N,N-二甲基胺基吡啶0.177g(1.45mmol)。接著，在滴加漏斗中，將二環己基碳二醯亞胺8.22g(39.84mmol)溶解於四氫呋喃50mL中，花30分鐘滴加，直接進行15小時反應。反應結束後，進行矽藻土過濾，將所得的濾液進行濃縮，添加乙酸乙酯300mL，以碳酸氫鈉水溶液進行2次分液洗滌，以水進行3次分液洗滌後，進行濃縮、真空乾燥，由此獲得橙色的黏稠液。將該黏稠液進行二氧化矽管柱純化(展開溶劑：己烷/乙酸乙酯 =80/20)，由此獲得化合物(7-3-1A)的白色結晶3.6g。 To a 1 L three-necked flask equipped with a dropping funnel, a thermometer, and a nitrogen introduction tube, 5.00 g (36.22 mmol) of hydroxybenzoic acid, 150 mL of tetrahydrofuran, 100 mL of third butanol, and 0.177 g of N, N-dimethylaminopyridine were added. (1.45 mmol). Next, in a dropping funnel, 8.22 g (39.84 mmol) of dicyclohexylcarbodiimide was dissolved in 50 mL of tetrahydrofuran, added dropwise over 30 minutes, and directly reacted for 15 hours. After the reaction was completed, diatomaceous earth was filtered, the obtained filtrate was concentrated, 300 mL of ethyl acetate was added, and the solution was separated and washed twice with aqueous sodium bicarbonate solution, and then separated and washed with water three times, and then concentrated and dried under vacuum. Thus, an orange viscous liquid was obtained. This viscous liquid was purified by silica column (developing solvent: hexane / ethyl acetate) = 80/20), whereby 3.6 g of a white crystal of the compound (7-3-1A) was obtained.

．化合物(7-3-1B)的合成． Synthesis of compound (7-3-1B)

在具備溫度計及氮氣導入管的500mL的三口燒瓶中，添加化合物(7-3-1A)12.25g(63.1mmol)、11-溴十一醇16.64g(66.2mmol)、N,N-二甲基乙醯胺180mL、碳酸鉀9.58g(69.4mmol)以及碘化鉀2.09g(12.6mmol)，在100℃進行2小時反應。反應結束後，添加乙酸乙酯500mL，以稀鹽酸進行1次分液洗滌，以水進行3次分液洗滌後，以硫酸鎂進行乾燥，並濃縮、脫水，由此獲得化合物(7-3-1B)的白色固體21.3g。 In a 500 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, 12.25 g (63.1 mmol) of compound (7-3-1A), 16.64 g (66.2 mmol) of 11-bromoundecanol, and N, N-dimethyl were added. 180 mL of acetamide, 9.58 g (69.4 mmol) of potassium carbonate, and 2.09 g (12.6 mmol) of potassium iodide were reacted at 100 ° C for 2 hours. After completion of the reaction, 500 mL of ethyl acetate was added, and the solution was washed with dilute hydrochloric acid once, and then washed with water three times, dried with magnesium sulfate, concentrated, and dehydrated to obtain a compound (7-3- 1B) 21.3 g of a white solid.

．化合物(7-3-1D)的合成． Synthesis of compound (7-3-1D)

在具備溫度計及氮氣導入管的1L的三口燒瓶中，添加化合物(7-3-1C)16.48g(58.4mmol)、化合物(7-3-1B)21.3g(58.4mmol)以及二氯甲烷440mL，使其懸浮，進行冰浴冷卻。接著，添加1-(3-二甲基胺基丙基)-3-乙基碳二醯亞胺鹽酸鹽13.47g(70.3mmol)、N,N-二甲基胺基吡啶1.43g(11.7mmol)，在冰浴冷卻下攪拌2小時後，恢復至室溫，進行16小時反應。反應結束後，添加乙酸乙酯2L，以水進行3次分液洗滌後，以硫酸鎂進行乾燥。接著，將濃縮而產生的白色析出物進行過濾、乾燥，由此獲得化合物(7-3-1D)的白色結晶26.0g。 In a 1 L three-necked flask equipped with a thermometer and a nitrogen introduction tube, 16.48 g (58.4 mmol) of compound (7-3-1C), 21.3 g (58.4 mmol) of compound (7-3-1B), and 440 mL of dichloromethane were added. This was suspended and cooled in an ice bath. Next, 13.47 g (70.3 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1.43 g of N, N-dimethylaminopyridine (11.7 mmol), stirred for 2 hours under cooling in an ice bath, then returned to room temperature, and reacted for 16 hours. After the reaction was completed, 2 L of ethyl acetate was added, and the mixture was washed with water three times, and then dried over magnesium sulfate. Next, the white precipitate produced by concentration was filtered and dried to obtain 26.0 g of a white crystal of the compound (7-3-1D).

．羧酸(7-3-1)的合成． Synthesis of carboxylic acid (7-3-1)

在500mL茄型燒瓶中，添加化合物(7-3-1D)26.0g(41.3mmol)、三氟乙酸55mL以及二氯甲烷110mL，在室溫下進行5 小時反應。反應結束後，利用抽吸機來去除溶劑後，添加乙酸乙酯2L以及四氫呋喃2L，以水洗滌3次後，以硫酸鎂進行乾燥。接著，將濃縮而產生的析出物進行過濾、乾燥，由此獲得羧酸(7-3-1)的白色結晶20.64g。 In a 500 mL eggplant-type flask, 26.0 g (41.3 mmol) of compound (7-3-1D), 55 mL of trifluoroacetic acid, and 110 mL of dichloromethane were added, and the reaction was performed at room temperature for 5 minutes. Hour response. After completion of the reaction, the solvent was removed with a suction machine, and 2 L of ethyl acetate and 2 L of tetrahydrofuran were added, washed three times with water, and then dried with magnesium sulfate. Next, the precipitate produced by concentration was filtered and dried to obtain 20.64 g of white crystals of a carboxylic acid (7-3-1).

[合成例14：含液晶配向性基的羧酸(8-1-1)的合成] [Synthesis Example 14: Synthesis of carboxylic acid (8-1-1) containing liquid crystal alignment group]

依據下述流程5來合成羧酸(8-1-1)。 The carboxylic acid (8-1-1) was synthesized according to the following scheme 5.

．化合物(8-1-1A)的合成． Synthesis of compound (8-1-1A)

在具備溫度計及氮氣導入管的1L的三口燒瓶中，添加化合物(6-6-1)15.0g、化合物(7-3-1B)16.6g以及二氯甲烷270mL，在5℃以下進行冰浴冷卻。接著，添加1-乙基-3-(3-二甲基胺基丙基)碳二醯亞胺鹽酸鹽10.47g、N,N-二甲基胺基吡啶1.11g，在5℃ 以下進行24小時反應。反應結束後，添加乙酸乙酯500mL、THF 250mL，以稀鹽酸進行1次分液洗滌，以水進行3次分液洗滌，以硫酸鎂進行乾燥後，加以濃縮而使其結晶化，由此獲得化合物(8-1-1A)的白色結晶18.4g(純度為100%)。 In a 1 L three-necked flask equipped with a thermometer and a nitrogen introduction tube, 15.0 g of the compound (6-6-1), 16.6 g of the compound (7-3-1B) and 270 mL of dichloromethane were added, and the solution was cooled in an ice bath at 5 ° C or lower. . Next, 10.47 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 1.11 g of N, N-dimethylaminopyridine were added at 5 ° C. The reaction was carried out for 24 hours. After completion of the reaction, 500 mL of ethyl acetate and 250 mL of THF were added, and the solution was washed with dilute hydrochloric acid once, and then washed with water three times, dried with magnesium sulfate, and concentrated to crystallize. 18.4 g of a compound (8-1-1A) as white crystals (purity: 100%).

．羧酸(8-1-1)的合成． Synthesis of carboxylic acid (8-1-1)

在具備氮氣導入管的500mL茄型燒瓶中，添加化合物(8-1-1A)18.4g、二氯甲烷90mL以及三氟乙酸45mL，在室溫下進行4小時反應。反應結束後，利用抽吸機來去除三氟乙酸後，溶解於乙酸乙酯600mL以及THF 300mL中，以水洗滌3次。接著，以硫酸鎂進行乾燥後，加以濃縮而使其結晶化，由此獲得羧酸(8-1-1)的白色結晶12.8g(純度為99.9%)。 In a 500 mL eggplant-type flask equipped with a nitrogen introduction tube, 18.4 g of the compound (8-1-1A), 90 mL of dichloromethane, and 45 mL of trifluoroacetic acid were added, and a reaction was performed at room temperature for 4 hours. After the reaction was completed, trifluoroacetic acid was removed using a suction machine, and then dissolved in 600 mL of ethyl acetate and 300 mL of THF, and washed three times with water. Next, magnesium sulfate was dried and then concentrated to crystallize, thereby obtaining 12.8 g (purity: 99.9%) of white crystals of a carboxylic acid (8-1-1).

[合成例15：含液晶配向性基的羧酸(9-1-1)的合成] [Synthesis Example 15: Synthesis of carboxylic acid (9-1-1) containing liquid crystal alignment group]

依據下述流程6來合成羧酸(9-1-1)。 The carboxylic acid (9-1-1) was synthesized according to the following scheme 6.

．化合物(9-1-1A)的合成． Synthesis of compound (9-1-1A)

利用與所述化合物(8-1-1)相同的方法來合成化合物(9-1-1A)。 The compound (9-1-1A) was synthesized by the same method as the compound (8-1-1).

．化合物(9-1-1B)的合成． Synthesis of compound (9-1-1B)

利用與所述化合物(7-3-1B)相同的方法來合成化合物(9-1-1B)。 The compound (9-1-1B) was synthesized by the same method as the compound (7-3-1B).

．化合物(9-1-1C)的合成． Synthesis of compound (9-1-1C)

在具備溫度計及氮氣導入管的100mL的三口燒瓶中，添加化合物(9-1-1A)3.4g、化合物(9-1-1B)2.2g以及二氯甲烷30mL，在5℃以下進行冰浴冷卻。接著，添加1-乙基-3-(3-二甲基胺基丙基)碳二醯亞胺鹽酸鹽1.7g、N,N-二甲基胺基吡啶0.18g，在5℃以下進行24小時反應。反應結束後，添加乙酸乙酯300mL，以水進行3次分液洗滌，以硫酸鎂進行乾燥後，加以濃縮而使其結晶化，由此獲得化合物(9-1-1C)的白色結晶2.4g。 In a 100 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, 3.4 g of compound (9-1-1A), 2.2 g of compound (9-1-1B), and 30 mL of dichloromethane were added, and the solution was cooled in an ice bath at 5 ° C or lower. . Next, 1.7 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.18 g of N, N-dimethylaminopyridine were added, and the temperature was 5 ° C or lower. 24 hours reaction. After the reaction was completed, 300 mL of ethyl acetate was added, and the mixture was washed with water three times. After drying with magnesium sulfate, the solution was concentrated and crystallized to obtain 2.4 g of white crystals of the compound (9-1-1C). .

．羧酸(9-1-1)的合成． Synthesis of carboxylic acid (9-1-1)

在100mL茄型燒瓶中，添加化合物(9-1-1C)2.4g、三氟乙酸4mL以及二氯甲烷8mL，在室溫下進行2小時反應。反應結束後，利用抽吸機來去除溶劑後，添加乙酸乙酯50mL以及四氫呋喃50mL，以水洗滌3次後，以硫酸鎂進行乾燥。接著，將濃縮而產生的析出物進行過濾、乾燥，由此獲得羧酸(9-1-1)的白色結晶1.7g。 In a 100 mL eggplant-type flask, 2.4 g of compound (9-1-1C), 4 mL of trifluoroacetic acid, and 8 mL of dichloromethane were added, and a reaction was performed at room temperature for 2 hours. After completion of the reaction, the solvent was removed with a suction machine, and then 50 mL of ethyl acetate and 50 mL of tetrahydrofuran were added, washed three times with water, and then dried with magnesium sulfate. Next, 1.7 g of white crystals of a carboxylic acid (9-1-1) were obtained by filtering and drying the precipitate produced by concentration.

[合成例16：含液晶配向性基的羧酸(10-1-1)的合成] [Synthesis Example 16: Synthesis of carboxylic acid (10-1-1) containing liquid crystal alignment group]

依據下述流程7來合成羧酸(10-1-1)。 The carboxylic acid (10-1-1) was synthesized according to the following scheme 7.

．化合物(10-1-1A)的合成． Synthesis of compound (10-1-1A)

利用與所述化合物(7-3-1)相同的方法來合成化合物(10-1-1A)。 The compound (10-1-1A) was synthesized by the same method as the compound (7-3-1).

．化合物(10-1-1B)的合成． Synthesis of compound (10-1-1B)

利用與化合物(7-3-1C)相同的方法來合成化合物(10-1-1B)。 The compound (10-1-1B) was synthesized by the same method as the compound (7-3-1C).

．化合物(10-1-1C)的合成． Synthesis of compound (10-1-1C)

在具備溫度計及氮氣導入管的300mL的三口燒瓶中，添加化合物(10-1-1A)9.21g(20mmol)、化合物(9-1-1B)5.89g(20mmol)以及二氯甲烷80mL，進行冰浴冷卻。接著，添加1-乙基 -3-(3-二甲基胺基丙基)碳二醯亞胺鹽酸鹽4.60g(24mmol)、N,N-二甲基胺基吡啶0.489g(4.0mmol)，在冰浴冷卻下攪拌4小時後，恢復為室溫，進行一晝夜的反應。反應結束後，添加乙酸乙酯1000mL，以水300mL進行4次分液洗滌後，以硫酸鎂進行乾燥。接著，將濃縮至100mL左右而產生的白色析出物進行過濾、乾燥，由此獲得化合物(10-1-1C)的白色結晶7.93g(純度為94.4%，產率為53.8%)。 In a 300 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, 9.21 g (20 mmol) of compound (10-1-1A), 5.89 g (20 mmol) of compound (9-1-1B), and 80 mL of dichloromethane were added, and the mixture was ice-cooled. The bath was cooled. Next, add 1-ethyl 3- (3-Dimethylaminopropyl) carbodiimide hydrochloride 4.60 g (24 mmol), N, N-dimethylaminopyridine 0.489 g (4.0 mmol), cooled in an ice bath After stirring for 4 hours, the temperature was returned to room temperature, and a reaction was performed throughout the day and night. After the reaction was completed, 1000 mL of ethyl acetate was added, and the solution was separated and washed 4 times with 300 mL of water, and then dried with magnesium sulfate. Next, a white precipitate produced by concentrating to about 100 mL was filtered and dried to obtain 7.93 g of a white crystal of the compound (10-1-1C) (purity: 94.4%, yield: 53.8%).

．羧酸(10-1-1)的合成． Synthesis of carboxylic acid (10-1-1)

在100mL茄型燒瓶中，添加化合物(10-1-1C)4.72g(6.41mmol)、三氟乙酸7mL以及二氯甲烷14mL，在室溫下進行1小時反應。反應結束後，利用抽吸機來去除溶劑後，添加乙酸乙酯100mL以及THF(加入有穩定劑)100mL，以水100mL洗滌3次後，以硫酸鎂進行乾燥。接著，添加數mg的聚合抑制劑，將濃縮至80mL左右而產生的析出物進行過濾、乾燥，由此獲得羧酸(10-1-1)的白色結晶2.59g(純度為97.2%，產率為59.4%)。 In a 100 mL eggplant-type flask, 4.72 g (6.41 mmol) of compound (10-1-1C), 7 mL of trifluoroacetic acid, and 14 mL of dichloromethane were added, and the reaction was performed at room temperature for 1 hour. After completion of the reaction, the solvent was removed by a suction machine, and 100 mL of ethyl acetate and 100 mL of THF (with a stabilizer added) were added. The solution was washed three times with 100 mL of water and then dried over magnesium sulfate. Next, several mg of a polymerization inhibitor was added, and the precipitate produced by concentration to about 80 mL was filtered and dried to obtain 2.59 g of white crystals of carboxylic acid (10-1-1) (purity: 97.2%, yield). 59.4%).

[合成例17：含配向性基的聚有機矽氧烷(S-2-5)的合成] [Synthesis Example 17: Synthesis of polyorganosiloxane (S-2-5) containing an alignment group]

在100mL的三口燒瓶中，投入所述合成例3中合成的聚有機矽氧烷(EPS-1)8.7g、甲基異丁基酮114g、化合物(6-6-1)2.7g(相對於聚有機矽氧烷(EPS-1)所具有的矽原子，相當於20莫耳%)、化合物(7-3-1)8.5g(相對於聚有機矽氧烷(EPS-1)所具有的矽原子，相當於30莫耳%)以及溴化四丁基銨0.89g，在 90℃進行30小時反應。反應結束後，在反應混合物中添加甲醇而生成沉澱，將使該沉澱物溶解於乙酸乙酯中而獲得的溶液水洗3次後，蒸餾去除溶劑，由此獲得聚有機矽氧烷(S-2-5)的白色粉末15g。聚有機矽氧烷(S-2-5)的重量平均分子量為9,500。 In a 100 mL three-necked flask, 8.7 g of the polyorganosiloxane (EPS-1) synthesized in Synthesis Example 3, 114 g of methyl isobutyl ketone, and 2.7 g of the compound (6-6-1) (in Silicon atom in polyorganosiloxane (EPS-1), equivalent to 20 mole%, and 8.5 g of compound (7-3-1) (compared with polyorganosiloxane (EPS-1) Silicon atom, equivalent to 30 mole%) and 0.89 g of tetrabutylammonium bromide, The reaction was carried out at 90 ° C for 30 hours. After the reaction was completed, methanol was added to the reaction mixture to generate a precipitate. The solution obtained by dissolving the precipitate in ethyl acetate was washed three times with water, and then the solvent was distilled off to obtain a polyorganosiloxane (S-2 -5) 15g of white powder. The weight average molecular weight of the polyorganosiloxane (S-2-5) was 9,500.

[合成例18~合成例21、合成例21A：含配向性基的聚有機矽氧烷的合成] [Synthesis Example 18 to Synthesis Example 21, Synthesis Example 21A: Synthesis of polyorganosiloxane containing an alignment group]

除了將所使用的化合物的種類及量設為如下述表4所述以外，利用與所述合成例17相同的方法來合成含配向性基的聚有機矽氧烷(S-2-6)~含配向性基的聚有機矽氧烷(S-2-9)、含配向性基的聚有機矽氧烷(S-2-11)。 A polyorganosiloxane (S-2-6) containing an alignment group was synthesized by the same method as in Synthesis Example 17 except that the types and amounts of the compounds used were as described in Table 4 below. Polyorganosiloxane containing alignment groups (S-2-9), Polyorganosiloxane containing alignment groups (S-2-11).

表4中，羧酸的調配量的數值表示相對於含環氧基的聚有機矽氧烷所具有的矽原子而言的投入量[莫耳%]。 In Table 4, the numerical value of the compounding quantity of a carboxylic acid shows the input amount [mol%] with respect to the silicon atom which the polyorganosiloxane containing an epoxy group has.

[合成例22：聚醯亞胺(P1-1)的合成] [Synthesis Example 22: Synthesis of Polyfluorene (P1-1)]

將作為四羧酸二酐的2,3,5-三羧基環戊基乙酸二酐19.1g、以及作為二胺的膽甾烷基氧基-2,4-二胺基苯(下述式(DA-1)所表示的化合物)8.49g及對苯二胺7.42g溶解於NMP 140g中，在60℃下進行4小時反應。將所得的聚醯胺酸溶液分取少量，添加NMP，以固體成分濃度為10%的溶液來測定黏度，結果，溶液黏度為100mPa．s。在所得的聚醯胺酸溶液中添加NMP 325g、吡啶6.74g及乙酸酐8.69g，在110℃下進行4小時脫水閉環。醯亞胺化反應後，利用新的NMP對系統內的溶劑進行溶劑置換(通過本操作，將醯亞胺化反應中使用的吡啶、乙酸酐去除至系統外)，獲得含有約15重量%的醯亞胺化率約50%的聚醯亞胺(PI-1)的溶液。 19.1 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride was And 8.49 g of cholestyloxy-2,4-diaminobenzene (a compound represented by the following formula (DA-1)) as a diamine and 7.42 g of p-phenylenediamine were dissolved in 140 g of NMP. The reaction was carried out at 60 ° C for 4 hours. A small amount of the obtained polyamic acid solution was added, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10%. As a result, the solution viscosity was 100 mPa. s. 325 g of NMP, 6.74 g of pyridine, and 8.69 g of acetic anhydride were added to the obtained polyamic acid solution, and dehydration and ring closure were performed at 110 ° C for 4 hours. After the amidine imidization reaction, the solvent in the system was replaced with a new NMP (by this operation, the pyridine and acetic anhydride used in the amidine imidization reaction were removed from the system) to obtain about 15% by weight A solution of polyfluorene imine (PI-1) having an imidization ratio of about 50%.

[實施例21] [Example 21] (1)液晶配向劑的製備 (1) Preparation of liquid crystal alignment agent

將作為聚合物成分的含配向性基的聚有機矽氧烷(S-2-5)200重量份及聚醯亞胺(PI-1)1,000重量份、以及作為化合物(D)的化合物(1-2-1)10重量份進行混合，向其中添加作為溶劑的 NMP以及丁基溶纖劑(BC)，製成溶劑組成為NMP：BC=50：50(重量比)、固體成分濃度為3.0重量%的溶液。利用孔徑為0.2μm的過濾器將該溶液進行過濾，由此製備液晶配向劑(A-21)。 200 parts by weight of an oriented polyorganosiloxane (S-2-5) as a polymer component, 1,000 parts by weight of a polyimide (PI-1), and a compound (1) as a compound (D) -2-1) 10 parts by weight are mixed and a solvent is added thereto NMP and butyl cellosolve (BC) were made into a solution with a solvent composition of NMP: BC = 50: 50 (weight ratio) and a solid content concentration of 3.0% by weight. This solution was filtered through a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (A-21).

(2)具有無圖案的透明電極的液晶顯示元件的製造 (2) Manufacturing of a liquid crystal display element having a patternless transparent electrode

使用所述製備的液晶配向劑(A-21)，來製造具有無圖案的透明電極的液晶顯示元件。首先，使用液晶配向膜印刷機(日本寫真印刷(股)製造)，在具有包含ITO膜的透明電極(無圖案)的玻璃基板的透明電極面上塗布液晶配向劑(A-21)。繼而，在80℃的加熱板上加熱(預烘烤)1分鐘而去除溶劑後，在150℃的加熱板上加熱(後烘烤)10分鐘，形成平均膜厚為600Å的塗膜。 The prepared liquid crystal alignment agent (A-21) was used to manufacture a liquid crystal display element having a transparent electrode without a pattern. First, using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.), a liquid crystal alignment agent (A-21) was coated on a transparent electrode surface of a glass substrate having a transparent electrode (unpatterned) including an ITO film. Then, after heating (pre-baking) on a hot plate at 80 ° C for 1 minute to remove the solvent, heating (post-baking) on a hot plate at 150 ° C for 10 minutes, a coating film having an average film thickness of 600Å was formed.

對於該塗膜，利用具有捲繞有人造絲布的輥的摩擦機器，以輥轉速400rpm、平臺移動速度3cm/秒、毛壓入長度0.1mm進行摩擦處理。然後，在超純水中進行1分鐘超音波洗滌，繼而在100℃潔淨烘箱中乾燥10分鐘，由此獲得具有液晶配向膜的基板。重複進行該操作，獲得具有液晶配向膜的一對(2塊)基板。 This coating film was subjected to a rubbing treatment using a rubbing machine having a roll around which a rayon cloth was wound, at a roll rotation speed of 400 rpm, a table moving speed of 3 cm / sec, and a gross press-in length of 0.1 mm. Then, ultrasonic washing was performed in ultrapure water for 1 minute, followed by drying in a 100 ° C clean oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of (two) substrates having a liquid crystal alignment film.

接著，在所述一對基板的具有液晶配向膜的各自的外緣，塗布加入有直徑為5.5μm的氧化鋁球的環氧樹脂黏接劑後，以液晶配向膜面相對的方式重疊而壓接，使黏接劑硬化。繼而，自液晶注入口向一對基板間填充向列型液晶(默克公司製造，MLC-6608)後，利用丙烯酸系光硬化黏接劑將液晶注入口密封，由此製造液晶顯示元件。 Next, the respective outer edges of the pair of substrates having the liquid crystal alignment film are coated with an epoxy resin adhesive with alumina balls having a diameter of 5.5 μm, and then the liquid crystal alignment films face each other and are pressed. Connect to harden the adhesive. Next, a nematic liquid crystal (Merck, 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 light-curing adhesive to produce a liquid crystal display element.

重複進行所述操作，製造3個具有無圖案的透明電極的液晶顯示元件。其中1個直接提供給後述的配向性的評價。對於其餘2個液晶顯示元件，分別利用下述方法(光照射步驟)，在對導電膜間施加電壓的狀態下進行光照射後，提供給配向性以及電壓保持率的評價。 Repeat the operation to produce 3 transparent electrodes with no pattern Liquid crystal display element. One of them is directly provided to the evaluation of alignment described later. For the remaining two liquid crystal display elements, the following method (light irradiation step) was used to perform light irradiation in a state where a voltage was applied between the conductive films, and then provided for evaluation of alignment and voltage retention.

(光照射步驟) (Light irradiation step)

對於所述獲得的3個液晶顯示元件中的2個，分別對電極間施加頻率為60Hz的交流10V，在液晶驅動的狀態下，使用將金屬鹵化物燈用作光源的紫外腺照射裝置，以100,000J/m²的照射量，自液晶顯示元件的外側來照射紫外線。此外，該照射量是使用以波長365nm為基準進行測量的光量計來測量的值。 For two of the three obtained liquid crystal display elements, an AC 10V having a frequency of 60 Hz was applied between the electrodes, and an ultraviolet gland irradiation device using a metal halide lamp as a light source was used in a state of liquid crystal driving to An irradiation amount of 100,000 J / m ² was irradiated with ultraviolet rays from the outside of the liquid crystal display element. In addition, this irradiation amount is a value measured using the light quantity meter which measured based on the wavelength of 365 nm.

(3)配向性的評價 (3) Evaluation of alignment

對於所述製造的3個液晶顯示元件，在背光照射下通過目視來觀察在不施加電壓的狀態下的漏光．配向混亂的有無。評價是以如下方法進行：將無漏光．配向混亂的情況評價為配向性「良」，將存在漏光．配向混亂的情況評價為配向性「不良」。其結果為，實施例21的3個液晶顯示元件均為配向性「良」。 For the three liquid crystal display elements manufactured as described above, light leakage was observed under a state of no voltage under a backlight. The presence of misalignment. The evaluation was performed as follows: there will be no light leakage. The alignment disorder is evaluated as "good" alignment, and there will be light leakage. The disordered alignment was evaluated as "bad" alignment. As a result, all three liquid crystal display elements of Example 21 had good alignment.

(4)電壓保持率的評價 (4) Evaluation of voltage holding ratio

在所述製造的3個液晶顯示元件中，對於光照射量為100,000J/m²的液晶顯示元件，在23℃下以60微秒的施加時間、167毫秒的跨距施加5V電壓後，測定自施加解除起167毫秒後的電壓保持率[%]。使用東陽特克尼卡(Toyo Technica)(股)製造的VHR-1作為測定裝置。其結果為，電壓保持率為98%。 Of the three liquid crystal display elements manufactured as described above, a liquid crystal display element having a light irradiation amount of 100,000 J / m ² was measured by applying a voltage of 5 V at 23 ° C. for an application time of 60 microseconds and a span of 167 milliseconds. Voltage retention [%] after 167 milliseconds since the release was applied. As a measuring device, VHR-1 manufactured by Toyo Technica Co., Ltd. was used. As a result, the voltage retention was 98%.

(5)具有經圖案化的透明電極的液晶顯示元件的製造 (5) Manufacturing of a liquid crystal display element having a patterned transparent electrode

使用所述製備的液晶配向劑(A-21)，來製造具有經圖案化的透明電極的液晶顯示元件。首先，在如圖2所示的分別具有經圖案化為狹縫狀、且被劃分為多個區域的ITO電極的一對玻璃基板(基板A、基板B)的各電極面上，使用液晶配向膜印刷機(日本寫真印刷(股)製造)來塗布液晶配向劑(A-21)。繼而，在80℃的加熱板上加熱(預烘烤)1分鐘而去除溶劑後，在150℃的加熱板上加熱(後烘烤)10分鐘，形成平均膜厚為600Å的塗膜。對於該塗膜，在超純水中進行1分鐘超音波洗滌後，在100℃潔淨烘箱中乾燥10分鐘，由此獲得具有液晶配向膜的一對(2塊)基板。 The prepared liquid crystal alignment agent (A-21) is used to manufacture a liquid crystal display element having a patterned transparent electrode. First, on each electrode surface of a pair of glass substrates (substrate A, substrate B) each having an ITO electrode patterned into a slit shape and divided into a plurality of regions as shown in FIG. 2, a liquid crystal alignment is used. A film printer (manufactured by Japan Photo Printing Co., Ltd.) to apply the liquid crystal alignment agent (A-21). Then, after heating (pre-baking) on a hot plate at 80 ° C for 1 minute to remove the solvent, heating (post-baking) on a hot plate at 150 ° C for 10 minutes, a coating film having an average film thickness of 600Å was formed. This coating film was subjected to ultrasonic washing in ultrapure water for 1 minute, and then dried in a 100 ° C. clean oven for 10 minutes, thereby obtaining a pair of (2) substrates having a liquid crystal alignment film.

繼而，在所述一對基板的具有液晶配向膜的各外緣，塗布加入有直徑為5.5μm的氧化鋁球的環氧樹脂黏接劑後，以液晶配向膜面相對的方式重疊而壓接，將黏接劑硬化。繼而，自液晶注入口向一對基板間填充向列型液晶(默克公司製造，MLC-6608)後，利用丙烯酸系光硬化黏接劑將液晶注入口密封，由此製造液晶顯示元件。 Then, the outer edges of the pair of substrates having the liquid crystal alignment film are coated with an epoxy resin adhesive with alumina balls having a diameter of 5.5 μm, and then the liquid crystal alignment film faces face each other and are crimped. To harden the adhesive. Next, a nematic liquid crystal (Merck, 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 light-curing adhesive to produce a liquid crystal display element.

重複進行所述操作，製造3個具有經圖案化的透明電極的液晶顯示元件。對於這些3個液晶顯示元件，以與製造所述具有無圖案的透明電極的液晶單元的情況相同的方式，在對導電膜間施加電壓的狀態下，以100,000J/m²的照射量照射紫外線，然後，進行響應速度的評價。此外，此處所使用的電極的圖案是與PSA模式的電極圖案為同一類的圖案。 This operation was repeated to manufacture three liquid crystal display elements having patterned transparent electrodes. For these three liquid crystal display elements, ultraviolet rays were irradiated with an irradiation amount of 100,000 J / m ² in a state where a voltage was applied between the conductive films in the same manner as in the case of manufacturing the liquid crystal cell having a patternless transparent electrode. Then, evaluate the response speed. The pattern of the electrode used here is the same pattern as the electrode pattern of the PSA mode.

(6)響應速度的評價 (6) Evaluation of response speed

對於所述製造的3個液晶顯示元件的每一個，首先不施加電壓而照射可見光燈，利用光萬用表(photo multimeter)來測定透過液晶顯示元件光的亮度。將此時的測定值作為相對透過率0%。接著，以與所述相同的方式來測定當對液晶顯示元件的電極間施加5秒的交流60V時的透過率(透過液晶顯示元件的光的亮度)，將該值作為相對透過率100%。然後，測定當對各液晶顯示元件施加交流60V時，相對透過率由10%過渡為90%為止的時間，將該時間定義為響應速度[msec]。此外，以3個單元的平均值來評價響應速度。其結果為，實施例21的液晶顯示元件的響應速度為10msec。 For each of the three liquid crystal display elements manufactured, first, a visible light lamp was irradiated without applying a voltage, and the brightness of light transmitted through the liquid crystal display element was measured using a photo multimeter. The measured value at this time was taken as a relative transmittance of 0%. Next, the transmittance (brightness of light transmitted through the liquid crystal display element) when AC 60 V was applied between the electrodes of the liquid crystal display element for 5 seconds was measured in the same manner as described above, and the relative transmittance was 100%. Then, the time until the relative transmittance transitioned from 10% to 90% when 60V AC was applied to each liquid crystal display element was measured, and this time was defined as the response speed [msec]. In addition, the response speed was evaluated by an average of 3 units. As a result, the response speed of the liquid crystal display element of Example 21 was 10 msec.

[實施例22~實施例26、比較例3] [Example 22 to Example 26, Comparative Example 3]

除了將所使用的聚合物(P)以及化合物(D)的種類及量變更為如下述表5所述以外，進行與實施例21相同的操作，由此製備液晶配向劑(A-22)~液晶配向劑(A-26)、液晶配向劑(R-3)。另外，使用所得的液晶配向劑(A-22)~液晶配向劑(A-26)、液晶配向劑(R-3)，以與實施例21相同的方式，來製造具有無圖案的透明電極的液晶顯示元件以及具有經圖案化的透明電極的液晶顯示元件，並且進行所述各種評價。將其結果示於下述表6中。 A liquid crystal alignment agent (A-22) was prepared by performing the same operation as in Example 21, except that the types and amounts of the polymer (P) and the compound (D) used were changed as described in Table 5 below. Liquid crystal alignment agent (A-26) and liquid crystal alignment agent (R-3). In addition, the obtained liquid crystal alignment agent (A-22) to liquid crystal alignment agent (A-26) and liquid crystal alignment agent (R-3) were used to produce a patternless transparent electrode in the same manner as in Example 21. A liquid crystal display element and a liquid crystal display element having a patterned transparent electrode were subjected to the various evaluations described above. The results are shown in Table 6 below.

表5中，各化合物的括弧內的數值表示各化合物的調配比例(重量份)。化合物(D)的略稱與表2相同。 In Table 5, the numerical value in parentheses of each compound represents the compounding ratio (part by weight) of each compound. The abbreviation of compound (D) is the same as in Table 2.

如表6所示，實施例21~實施例26的液晶顯示元件均為液晶配向性為「良」的評價。另外，電壓保持率高至98%以上，響應速度也快。於此相對，比較例3中，液晶配向性以及響應速度雖與實施例為同等，但電壓保持率低至95%。 As shown in Table 6, the liquid crystal display elements of Examples 21 to 26 were all evaluated as having "good" liquid crystal alignment. In addition, the voltage retention rate is as high as 98% and the response speed is fast. In contrast, in Comparative Example 3, although the liquid crystal alignment and response speed were equivalent to those of the Example, the voltage retention rate was as low as 95%.

Claims

一種液晶配向劑，其含有：聚合物成分、及下述式(1)所表示的化合物(D)，所述聚合物成分含有含環氧基的聚合物，並且相對於所述液晶配向劑中的所述聚合物成分的總體100重量份，所述化合物(D)的含量為1重量份~30重量份，(式(1)中，A¹為包含聚合性不飽和鍵的基團，A²為可與環氧基進行反應的官能基，R¹為(m+n)價的經醚基取代的鏈狀烴基；m為2~18的整數，n為1~18的整數；其中，滿足(m+n)≦20)。A liquid crystal alignment agent comprising a polymer component and a compound (D) represented by the following formula (1), wherein the polymer component contains an epoxy-group-containing polymer and is contained in the liquid crystal alignment agent; 100 parts by weight of the polymer component as a whole, and the content of the compound (D) is 1 to 30 parts by weight, (In formula (1), A ¹ is a group containing a polymerizable unsaturated bond, A ² is a functional group capable of reacting with an epoxy group, and R ¹ is a (m + n) -valent ether-substituted chain Like hydrocarbon group; m is an integer of 2 to 18, n is an integer of 1 to 18, wherein (m + n) ≦ 20) is satisfied.

如申請專利範圍第1項所述的液晶配向劑，其中所述n為2~18的整數。The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein n is an integer from 2 to 18.

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A¹為選自由(甲基)丙烯醯基氧基、乙烯基及苯乙烯基所組成的組群中的至少一種。The liquid crystal alignment agent according to item 1 or item 2 of the patent application scope, wherein the A ¹ is at least ^one selected from the group consisting of a (meth) acrylfluorenyloxy group, a vinyl group, and a styryl group. One.

如申請專利範圍第1項或第2項所述的液晶配向劑，其含有選自由聚醯胺酸、聚醯胺酸酯、聚醯亞胺及聚有機矽氧烷所組成的組群中的至少一種作為所述聚合物成分。The liquid crystal alignment agent according to item 1 or item 2 of the scope of the patent application, which contains a liquid crystal alignment agent selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyorganosiloxane. At least one is used as the polymer component.

如申請專利範圍第1項或第2項所述的液晶配向劑，其含有含環氧基的聚有機矽氧烷作為所述聚合物成分。The liquid crystal alignment agent according to item 1 or item 2 of the patent application scope, which contains an epoxy-group-containing polyorganosiloxane as the polymer component.

一種液晶配向膜，其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。A liquid crystal alignment film is formed using the liquid crystal alignment agent according to any one of claims 1 to 5 in the scope of patent application.

一種液晶配向膜的製造方法，其包括：在基板上塗布如申請專利範圍第1項至第5項中任一項所述的液晶配向劑而形成塗膜的步驟；以及對所述塗膜進行光照射的步驟。A method for manufacturing a liquid crystal alignment film, comprising: applying a liquid crystal alignment agent according to any one of claims 1 to 5 on a substrate to form a coating film; and performing a coating film on the substrate; Steps of light irradiation.

一種液晶顯示元件，其包括如申請專利範圍第6項所述的液晶配向膜或者利用如申請專利範圍第7項所述的液晶配向膜的製造方法而獲得的液晶配向膜。A liquid crystal display element includes the liquid crystal alignment film according to item 6 of the patent application scope or a liquid crystal alignment film obtained by using the manufacturing method of the liquid crystal alignment film according to item 7 of the patent application scope.

一種液晶顯示元件的製造方法，其包括：在一對基板的各表面上分別塗布如申請專利範圍第1項至第5項中任一項所述的液晶配向劑，繼而對其進行加熱而形成塗膜的步驟；以所述塗膜相對的方式，將形成有所述塗膜的一對基板隔著液晶分子的層而對向配置，來構築液晶單元的步驟；以及自所述液晶單元的外側進行光照射的步驟。A method for manufacturing a liquid crystal display element, comprising: coating a liquid crystal alignment agent according to any one of claims 1 to 5 on a surface of a pair of substrates, and then heating the liquid crystal alignment agent to form a liquid crystal display element. A step of coating a film; a step of constructing a liquid crystal cell by arranging a pair of substrates on which the coating film is formed so as to face each other with a layer of liquid crystal molecules facing the coating film; and Step of performing light irradiation on the outside.