TWI834646B

TWI834646B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

Info

Publication number: TWI834646B
Application number: TW108109269A
Authority: TW
Inventors: 別府功一朗; 須賀貴裕; 相馬早紀
Original assignee: 日商日產化學股份有限公司
Priority date: 2018-03-19
Filing date: 2019-03-19
Publication date: 2024-03-11
Also published as: CN117148630A; JP7334723B2; KR20200132908A; CN111868620A; TW201947028A; WO2019181879A1; CN111868620B; JPWO2019181879A1

Abstract

提供一種能夠得到電壓保持率為優異、累積電荷的緩和為快速、且液晶配向性或透明性為良好的液晶配向膜的液晶配向劑、液晶配向膜及液晶顯示元件。本發明的液晶配向劑，其特徵在於含有下述(A)成分、(B)成分及有機溶劑， (A)成分：選自由聚醯亞胺前驅物、該聚醯亞胺前驅物的醯亞胺化聚合物及在100~300℃的溫度範圍內展現出液晶性的感光性側鏈型丙烯酸聚合物所成的群組中的至少1種的聚合物； (B)成分：下述式(1)所表示的化合物， (Q¹ 、Q² 為(Q1-1)等，Q¹ 、Q² 中的任一者為(Q1-1)) (q1、q2為0或1，R¹ 為氫原子等，R² 、R³ 為具有環氧部位的基等，R² 、R³ 中的任一者為具有環氧部位的基)。Provided are a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element that can obtain a liquid crystal alignment film that has excellent voltage retention, rapid relaxation of accumulated charges, and good liquid crystal alignment or transparency. The liquid crystal alignment agent of the present invention is characterized by containing the following components (A), (B) and an organic solvent. (A) component: a polyimide precursor, and an imide selected from the polyimide precursor. At least one polymer from the group consisting of aminated polymers and photosensitive side chain acrylic polymers that exhibit liquid crystallinity in the temperature range of 100 to 300°C; (B) Component: the following formula ( 1) The compound represented by (Q ¹ and Q ² are (Q1-1), etc., and either Q ¹ or Q ² is (Q1-1)) (q1 and q2 are 0 or 1, R ¹ is a hydrogen atom, etc., R ² and R ³ are groups having an epoxy moiety, etc., and either R ² or R ³ is a group having an epoxy moiety).

Description

液晶配向劑、液晶配向膜及液晶顯示元件Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

本發明為關於新穎液晶配向劑、液晶配向膜及使用其的液晶顯示元件。The present invention relates to novel liquid crystal alignment agents, liquid crystal alignment films and liquid crystal display elements using the same.

液晶顯示元件廣泛用作電腦、手機、智慧手機、電視等的顯示部。液晶顯示元件具備例如：夾在元件基板和濾色片基板之間的液晶層、對液晶層施加電場的像素電極和共用電極、控制液晶層的液晶分子的配向性的配向膜、切換提供給像素電極的電信號的薄膜電晶體(TFT)等。作為液晶分子的驅動方式，已知有TN方式、VA方式等的縱向電場方式、或IPS方式、FFS方式等的橫向電場方式。相較於以往的對形成在上下基板上的電極施加電壓來驅動液晶的「縱向電場方式」，僅在基板的單側形成電極並以平行於基板的方向來施加電場的「橫向電場方式」具有較廣的視野角特性，又，已知能作為高品位顯示的液晶顯示元件。Liquid crystal display elements are widely used as display parts for computers, mobile phones, smartphones, televisions, etc. A liquid crystal display element includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode that apply an electric field to the liquid crystal layer, an alignment film that controls the alignment of liquid crystal molecules in the liquid crystal layer, and a switching supply to the pixels. Thin film transistor (TFT) for electrical signals of electrodes, etc. As a driving method of liquid crystal molecules, longitudinal electric field methods such as TN method and VA method, or transverse electric field methods such as IPS method and FFS method are known. Compared with the conventional "vertical electric field method" in which voltage is applied to electrodes formed on upper and lower substrates to drive liquid crystals, the "transverse electric field method" in which electrodes are formed on only one side of the substrate and an electric field is applied in a direction parallel to the substrate has It has wide viewing angle characteristics and is known to be a liquid crystal display element capable of high-quality display.

即便是橫向電場方式的液晶晶胞(liquid crystal cell)的視野角特性為優異，但由於形成在基板內的電極部分較少，所以如果電壓保持率低的話，則不會對液晶施加足夠的電壓，而顯示的對比度會降低。此外，如果液晶配向的穩定性小的話，則長時間驅動液晶時，液晶變得不會回復到初期狀態，而成為對比度降低、殘影的原因，因此液晶配向的穩定性為重要的。進而，靜電容易在液晶晶胞內累積，即便是利用施加由驅動所產生的正負不對稱電壓，電荷仍會累積在液晶晶胞內，該等被累積的電荷會以液晶配向紊亂或殘影的形式來影響顯示，而使得液晶元件的顯示品位會明顯地降低。Even if a transverse electric field type liquid crystal cell has excellent viewing angle characteristics, since there are few electrode parts formed in the substrate, if the voltage retention rate is low, sufficient voltage will not be applied to the liquid crystal. , and the display contrast will be reduced. In addition, if the stability of the liquid crystal alignment is small, the liquid crystal will not return to the initial state when the liquid crystal is driven for a long time, causing a decrease in contrast and image sticking. Therefore, the stability of the liquid crystal alignment is important. Furthermore, static electricity is easy to accumulate in the liquid crystal cell. Even if a positive and negative asymmetric voltage generated by driving is applied, charges will still accumulate in the liquid crystal cell. The accumulated charges will cause liquid crystal alignment disorder or image sticking. The form will affect the display, and the display quality of the liquid crystal element will be significantly reduced.

在如此般的橫向電場方式的液晶顯示元件中使用時，作為電壓保持率為優異、且電荷累積為降低的液晶配向劑，專利文獻1中揭示了一種含有特定的二胺與脂肪族四羧酸衍生物的液晶配向劑。另外，作為縮短至殘影消失為止的時間之方法，提案了使用如專利文獻2的體積電阻率為低的配向膜之方法、或使用如專利文獻3的體積電阻率不易受到液晶顯示元件的背光而產生變化的配向膜之方法。然而，隨著液晶顯示元件的高性能化，液晶配向膜所要求的特性也變得嚴格，該等的以往技術仍難以充分滿足所有的要求特性。 [先前技術文獻] [專利文獻]When used in such a transverse electric field type liquid crystal display element, Patent Document 1 discloses a liquid crystal alignment agent containing a specific diamine and an aliphatic tetracarboxylic acid as a liquid crystal alignment agent that has excellent voltage retention and reduced charge accumulation. Derivative liquid crystal alignment agent. In addition, as a method of shortening the time until the afterimage disappears, it is proposed to use an alignment film with a low volume resistivity as in Patent Document 2, or to use a liquid crystal display element with a volume resistivity that is less susceptible to backlight as in Patent Document 3. The method of producing a changed alignment film. However, as the performance of liquid crystal display elements increases, the characteristics required of liquid crystal alignment films have become stricter, and it is still difficult for these conventional technologies to fully meet all the required characteristics. [Prior technical literature] [Patent Document]

[專利文獻1]國際公開(WO)2004/021076號說明書 [專利文獻2]國際公開(WO)2004/053583號說明書 [專利文獻3]國際公開(WO)2013/008822號說明書[Patent Document 1] International Publication (WO) No. 2004/021076 Specification [Patent Document 2] International Publication (WO) No. 2004/053583 Specification [Patent Document 3] International Publication (WO) No. 2013/008822

[發明所欲解決之課題][Problem to be solved by the invention]

本發明之課題為提供一種能夠得到電壓保持率為優異、累積電荷的緩和為快速、且液晶配向性或透明性為良好的液晶配向膜的液晶配向劑、液晶配向膜及液晶顯示元件。 [解決課題之手段]An object of the present invention is to provide a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element that can provide a liquid crystal alignment film that has excellent voltage retention, rapid relaxation of accumulated charges, and good liquid crystal alignment or transparency. [Means to solve the problem]

本發明人為了解決上述課題經深入研究之結果遂而完成本發明。本發明為一種液晶配向劑，其特徵在於含有下述(A)成分、(B)成分及有機溶劑。 (A)成分：聚合物 (B)成分：下述式(1)所表示的化合物 (式中，Q¹ 及Q² 為選自下述(Q1-1)及單鍵中的1種，Q¹ 及Q² 的至少1個為(Q1-1)， q1及q2分別獨立為0或1， R¹ 為氫原子或一價有機基， R² 及R³ 分別獨立為具有環氧部位的基及氫原子中的任一者，R² 及R³ 的至少1個為具有環氧部位的基)。 [發明的效果]The present inventor completed the present invention as a result of in-depth research in order to solve the above-mentioned problems. The present invention is a liquid crystal alignment agent, characterized by containing the following components (A), (B) and an organic solvent. (A) component: polymer (B) component: compound represented by the following formula (1) (In the formula, Q ¹ and Q ² are one selected from the following (Q1-1) and single bonds, and at least one of Q ¹ and Q ² is (Q1-1), q1 and q2 are independently 0 or 1, R ¹ is a hydrogen atom or a monovalent organic group, R ² and R ³ are independently any one of a group having an epoxy site and a hydrogen atom, R ² and R ³ At least one group has an epoxy moiety). [Effects of the invention]

藉由本發明的液晶配向劑，可提供電壓保持率為優異、累積電荷的緩和為快速、且液晶配向性或透明性為良好的液晶配向膜及顯示特性為優異的液晶顯示元件。藉由本案發明而能夠解決上述課題之理由尚不明確，但大致上可認為是如下述。本發明的液晶配向劑中所含有的上述式(1)所表示的化合物的構造，係具有共軛構造。因此，例如在液晶配向膜中係能夠促進電荷的移動，並能夠促進累積電荷的緩和。The liquid crystal alignment agent of the present invention can provide a liquid crystal alignment film with excellent voltage retention, rapid relaxation of accumulated charges, good liquid crystal alignment or transparency, and a liquid crystal display element with excellent display characteristics. The reason why the above-mentioned problems can be solved by the present invention is not yet clear, but it is generally considered as follows. The structure of the compound represented by the above formula (1) contained in the liquid crystal alignment agent of the present invention has a conjugated structure. Therefore, for example, in a liquid crystal alignment film, the movement of charges can be promoted and the relaxation of accumulated charges can be promoted.

[實施發明之最佳形態][The best way to implement the invention]

＜(A)成分＞本發明的液晶配向劑中所包含的(A)成分，其係選自由聚醯亞胺前驅物、該聚醯亞胺前驅物的醯亞胺化聚合物及在指定的溫度範圍內展現出液晶性的感光性側鏈型丙烯酸聚合物所成的群組中的至少1種的聚合物。＜(A)Component＞ The (A) component contained in the liquid crystal alignment agent of the present invention is selected from a polyimide precursor, an imidized polymer of the polyimide precursor, and exhibits liquid crystals within a specified temperature range. At least one polymer from the group of photosensitive side chain acrylic polymers.

＜聚醯亞胺前驅物＞ (A)成分的聚醯亞胺前驅物具有下述式(A1)所表示的構造單位。 <Polyimide precursor> The polyimide precursor of component (A) has a structural unit represented by the following formula (A1).

式(A1)中，X₁ 為四價有機基，Y₁ 為二價有機基。 R₁ 為氫原子或碳數1~5的烷基，A₁ 及A₂ 分別獨立為氫原子、可具有取代基的碳數1~10的烷基、可具有取代基的碳數2~10的烯基或可具有取代基的碳數2~10的炔基。作為R₁ 中的烷基的具體例，可舉出甲基、乙基、丙基、i-丙基、n-丁基、i-丁基、s-丁基、t-丁基、n-戊基等。就藉由加熱而可容易醯亞胺化之觀點而言，R₁ 較佳為氫原子或甲基。In formula (A1), X ₁ is a tetravalent organic group, and Y ₁ is a divalent organic group. R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A ₁ and A ₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and an alkyl group having 2 to 10 carbon atoms which may have a substituent. An alkenyl group or an alkynyl group having 2 to 10 carbon atoms which may have a substituent. Specific examples of the alkyl group in R ₁ include methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n- Pentyl etc. From the viewpoint of being easily imidized by heating, R ₁ is preferably a hydrogen atom or a methyl group.

X₁ 為源自於四羧酸衍生物的四價有機基，該構造並無特別限定。聚醯亞胺前驅物中，亦可混合存在2種類以上的X₁ 。作為X₁ 的具體例，可舉出下述式(X-1)~(X-44)的構造。 X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and the structure is not particularly limited. In the polyimide precursor, two or more types of X ₁ may be mixed. Specific examples of X ₁ include structures of the following formulas (X-1) to (X-44).

上述式(X-1)中的R₈ ~R₁₁ 分別獨立為氫原子、鹵素原子、碳數1~6的烷基、碳數2~6的烯基、碳數2~6的炔基或苯基。若R₈ ~R₁₁ 為大體積的構造時，有可能會使液晶配向性降低，故又較佳為氫原子、甲基或乙基，特佳為氫原子或甲基。R ₈ ~ R ₁₁ in the above formula (X-1) are independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, or phenyl. If R ₈ ~ R ₁₁ have a large volume structure, the liquid crystal alignment may be reduced, so a hydrogen atom, a methyl group or an ethyl group is preferred, and a hydrogen atom or a methyl group is particularly preferred.

作為X₁ ，就單體的取得性之觀點而言，較佳為選自式(X-1)~(X-14)中的構造。作為上述選自式(X-1)~(X-14)中的構造的較佳的比例，係X₁ 整體的20莫耳%以上，又較佳為60莫耳%以上，更佳為80莫耳%以上。X ₁ is preferably a structure selected from the group consisting of formulas (X-1) to (X-14) from the viewpoint of monomer availability. As a preferable ratio of the structure selected from the above formulas (X-1) to (X-14), it is 20 mol% or more of the entire _X1 , preferably 60 mol% or more, and more preferably 80 More than mol%.

A₁ 及A₂ 分別獨立為氫原子、可具有取代基的碳數1~10的烷基、可具有取代基的碳數2~10的烯基或可具有取代基的碳數2~10的炔基。作為上述烷基的具體例，可舉出甲基、乙基、丙基、丁基、t-丁基、己基、辛基、癸基、環戊基、環己基、雙環己基等。A ₁ and A ₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, or an alkenyl group having 2 to 10 carbon atoms which may have a substituent. Alkynyl. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, t-butyl, hexyl, octyl, decyl, cyclopentyl, cyclohexyl, bicyclohexyl, and the like.

作為烯基，可舉出將上述烷基中存在的1個以上的CH₂ -CH₂ 構造取代成為CH＝CH構造而成的構造。具體而言可舉出乙烯基、烯丙基、1-丙烯基、異丙烯基、2-丁烯基、1,3-丁二烯基、2-戊烯基、2-己烯基、環丙烯基、環戊烯基、環己烯基等。作為炔基，可舉出將存在於前述的烷基之1個以上的CH₂ -CH₂ 構造取代成C≡C構造者。具體而言可舉出乙炔基、1-丙炔基、2-丙炔基等。Examples of the alkenyl group include a structure in which one or more CH ₂ -CH ₂ structures present in the alkyl group are substituted with a CH=CH structure. Specific examples include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclo propenyl, cyclopentenyl, cyclohexenyl, etc. Examples of the alkynyl group include those in which one or more CH ₂ -CH ₂ structures present in the aforementioned alkyl groups are substituted with a C≡C structure. Specific examples include ethynyl, 1-propynyl, 2-propynyl, and the like.

上述的烷基、烯基、及炔基亦可具有取代基，進而亦可藉由取代基來形成環構造。尚，所謂藉由取代基來形成環構造係指取代基彼此或取代基與母骨架的一部分鍵結而成為環構造之涵義。作為上述取代基之例子，可舉出鹵素基、羥基、硫醇基、硝基、芳基、有機氧基、有機硫基、有機矽烷基、醯基、酯基、硫酯基、磷酸酯基、醯胺基、烷基、烯基、炔基等。The above-mentioned alkyl group, alkenyl group, and alkynyl group may have a substituent, and further may form a ring structure through the substituent. Note that the formation of a ring structure by substituents means that the substituents are bonded to each other or to a part of the parent skeleton to form a ring structure. Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organic oxygen group, an organic thio group, an organic silyl group, a hydroxyl group, an ester group, a thioester group, and a phosphate group. , amide group, alkyl group, alkenyl group, alkynyl group, etc.

作為取代基的鹵素基，可舉出氟原子、氯原子、溴原子或碘原子。作為取代基的芳基，可舉出苯基。該芳基可進一步被前述的其他的取代基取代。Examples of the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the aryl group as a substituent include phenyl. The aryl group may be further substituted by other substituents mentioned above.

取代基的有機氧基，可由-O-R所表示的構造來表示。該R可為相同或相異，可示例如前述的烷基、烯基、炔基、芳基等。該等的R可進一步被前述的取代基取代。作為有機氧基的具體例，可舉出甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基等。The organic oxygen group of the substituent can be represented by the structure represented by -O-R. The R may be the same or different, and may be exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, etc. These R may be further substituted by the aforementioned substituents. Specific examples of the organic oxygen group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, and the like.

取代基的有機硫基，可由-S-R所表示的構造來表示。作為該R可示例如前述的烷基、烯基、炔基、芳基等。該等的R可進一步被前述的取代基取代。作為有機硫基的具體例，可舉出甲硫基、乙硫基、丙硫基、丁硫基、戊硫基、己硫基、庚硫基、辛硫基等。The organic sulfide group of the substituent can be represented by the structure represented by -S-R. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These R may be further substituted by the aforementioned substituents. Specific examples of the organic sulfide group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, and the like.

取代基的有機矽烷基，可由-Si-(R)₃ 所表示的構造來表示。該R可為相同或相異，可示例如前述的烷基、烯基、炔基、芳基等。該等的R可進一步被前述的取代基取代。作為有機矽烷基的具體例，可舉出三甲基甲矽烷基、三乙基甲矽烷基、三丙基甲矽烷基、三丁基甲矽烷基、三戊基甲矽烷基、三己基甲矽烷基、戊基二甲基甲矽烷基、己基二甲基甲矽烷基等。The organosilyl group of the substituent can be represented by the structure represented by -Si-(R) ₃ . The R may be the same or different, and may be exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, etc. These R may be further substituted by the aforementioned substituents. Specific examples of the organosilyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, and trihexylsilyl group. Pentyldimethylsilyl, hexyldimethylsilyl, etc.

取代基的醯基，可由-C(O)-R所表示的構造來表示。作為該R可示例如前述的烷基、烯基、芳基等。該等的R可進一步被前述的取代基取代。作為醯基的具體例，可舉出甲醯基、乙醯基、丙醯基、丁醯基、異丁醯基、戊醯基、異戊醯基、苯甲醯基等。The hydroxyl group of the substituent can be represented by the structure represented by -C(O)-R. Examples of R include the aforementioned alkyl group, alkenyl group, aryl group, and the like. These R may be further substituted by the aforementioned substituents. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butylyl group, an isobutylyl group, a pentyl group, an isopentyl group, a benzyl group, and the like.

取代基的酯基，可由-C(O)O-R或-OC(O)-R所表示的構造來表示。作為該R可示例如前述的烷基、烯基、炔基、芳基等。該等的R可進一步被前述的取代基取代。The ester group of the substituent can be represented by a structure represented by -C(O)O-R or -OC(O)-R. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These R may be further substituted by the aforementioned substituents.

取代基的硫酯基，可由-C(S)O-R、或 -OC(S)-R所表示的構造來表示。作為該R可示例如前述的烷基、烯基、炔基、芳基等。該等的R可進一步被前述的取代基取代。The thioester group of the substituent can be -C(S)O-R, or -OC(S)-R represents the structure represented. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These R may be further substituted by the aforementioned substituents.

取代基的磷酸酯基，可由-OP(O)-(OR)₂ 所表示的構造來表示。該R可為相同或相異，可示例如前述的烷基、烯基、炔基、芳基等。該等的R可進一步被前述的取代基取代。The phosphate group of the substituent can be represented by the structure represented by -OP(O)-(OR) ₂ . The R may be the same or different, and may be exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, etc. These R may be further substituted by the aforementioned substituents.

取代基的醯胺基，可由-C(O)NH₂ 、或 -C(O)NHR、-NHC(O)R、-C(O)N(R)₂ 、-NRC(O)R所表示的構造來表示。該R可為相同或相異，可示例如前述的烷基、烯基、炔基、芳基等。該等的R可進一步被前述的取代基取代。The amide group of the substituent can be represented by -C(O)NH ₂ , or -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ , or -NRC(O)R structure to represent. The R may be the same or different, and may be exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, etc. These R may be further substituted by the aforementioned substituents.

取代基的芳基，可舉出與前述的芳基為相同者。該芳基可進一步被前述的其他的取代基取代。取代基的烷基，可舉出與前述的烷基為相同者。該烷基可進一步被前述的其他的取代基取代。取代基的烯基，可舉出與前述的烯基為相同者。該烯基可進一步被前述的其他的取代基取代。取代基的炔基，可舉出與前述的炔基為相同者。該炔基可進一步被前述的其他的取代基取代。The aryl group of the substituent is the same as the aryl group mentioned above. The aryl group may be further substituted by other substituents mentioned above. The alkyl group of the substituent is the same as the alkyl group mentioned above. The alkyl group may be further substituted by other substituents mentioned above. Examples of the alkenyl group of the substituent include the same alkenyl groups as mentioned above. The alkenyl group may be further substituted by other substituents mentioned above. The alkynyl group of the substituent is the same as the alkynyl group mentioned above. The alkynyl group may be further substituted by other substituents mentioned above.

通常，若導入體積大的構造時，會有使胺基的反應性或液晶配向性降低之可能性，因此，作為A₁ 及A₂ 係以氫原子、或可具有取代基的碳數1~5的烷基為又較佳，以氫原子、甲基或乙基為特佳。Generally, when a bulky structure is introduced, the reactivity or liquid crystal alignment of the amine group may be reduced. Therefore, A ₁ and A ₂ are hydrogen atoms or carbon atoms that may have substituents from 1 to The alkyl group of 5 is more preferred, and hydrogen atom, methyl or ethyl group is particularly preferred.

Y₁ 係源自於二胺的二價有機基，該構造並無特別限定。作為Y₁ 的具體例可舉出下述式(Y-1)~(Y-119)。 Y ₁ is a divalent organic group derived from diamine, and the structure is not particularly limited. Specific examples of Y ₁ include the following formulas (Y-1) to (Y-119).

式(Y-109)中，m及n分別為1~11的整數，m＋n為2~12的整數。式(Y-114)中，h為1~3的整數，式(Y-111)及(Y-117)中，j為0~3的整數。作為Y₁ ，就所得到的液晶配向膜的液晶配向性或預傾角之觀點而言，以選自下述式(5)及(6)所表示的構造中之至少1種為又較佳。式(5)中，R₁₂ 為單鍵或碳數1~30的二價有機基，R₁₃ 為氫原子、鹵素原子或碳數1~30的一價有機基，a為1~4的整數。當a為2以上時，R₁₂ 及R₁₃ 互相可為相同或相異。式(6)中，R₁₄ 為單鍵、-O-、-S-、-NR₁₅ -、醯胺鍵、酯鍵、尿素鍵或碳數1~40的二價有機基，R₁₅ 為氫原子或甲基。In formula (Y-109), m and n are integers from 1 to 11 respectively, and m+n is an integer from 2 to 12. In formula (Y-114), h is an integer from 1 to 3, and in formulas (Y-111) and (Y-117), j is an integer from 0 to 3. As Y ₁ , from the viewpoint of liquid crystal alignment or pretilt angle of the obtained liquid crystal alignment film, at least one selected from the structures represented by the following formulas (5) and (6) is more preferred. In formula (5), R ₁₂ is a single bond or a divalent organic group with 1 to 30 carbon atoms, R ₁₃ is a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 30 carbon atoms, and a is an integer from 1 to 4. . When a is 2 or more, R ₁₂ and R ₁₃ may be the same or different from each other. In formula (6), R ₁₄ is a single bond, -O-, -S-, -NR ₁₅ -, amide bond, ester bond, urea bond or a divalent organic group with 1 to 40 carbon atoms, and R ₁₅ is hydrogen. atom or methyl group.

作為式(5)及式(6)所表示的Y₁ 的具體例，在前述式(Y-1)~(Y-119)之中，可舉出以下的構造。高直線性的構造的Y₁ ，於製成液晶配向膜時可提高液晶的配向性，因此以式(Y-7)、(Y-21)、(Y-22)、(Y-23)、(Y-25)、(Y-43)、(Y-44)、(Y-45)、(Y-46)、(Y-48)、(Y-63)、(Y-71)、(Y-72)、(Y-73)、(Y-74)、 (Y-75)、(Y-98)、(Y-99)、(Y-100)、或(Y-118)為較佳。可提高液晶的配向性的上述Y₁ 的構造的比例，以Y₁ 整體的20莫耳%以上為較佳，又較佳為60莫耳%以上，更佳為80莫耳%以上。As specific examples of Y ₁ represented by formula (5) and formula (6), among the aforementioned formulas (Y-1) to (Y-119), the following structures can be cited. Y ₁ with a highly linear structure can improve the alignment of liquid crystal when making a liquid crystal alignment film. Therefore, the formulas (Y-7), (Y-21), (Y-22), (Y-23), (Y-25), (Y-43), (Y-44), (Y-45), (Y-46), (Y-48), (Y-63), (Y-71), (Y -72), (Y-73), (Y-74), (Y-75), (Y-98), (Y-99), (Y-100), or (Y-118) are preferred. The proportion of the structure of Y ₁ that can improve the alignment of liquid crystal is preferably 20 mol% or more of the total Y ₁ , more preferably 60 mol% or more, and more preferably 80 mol% or more.

於製成液晶配向膜時，欲提高液晶的預傾角的話，作為Y₁ ，較佳為在側鏈具有長鏈烷基、芳香族環、脂肪族環、類固醇骨架、或組合該等的構造。作為如此般的Y₁ ，以式(Y-76)~(Y-97)為較佳。欲提高預傾角時之上述Y₁ 的構造的比例，以Y₁ 整體的1~30莫耳%為較佳，以1~20莫耳%為又較佳。又，作為(A)成分的聚合物，若使用具有光配向性側鏈的聚醯亞胺前驅物或者聚醯亞胺時，該聚醯亞胺前驅物或者聚醯亞胺係以具有下述的光反應性側鏈為較佳。When forming a liquid crystal alignment film, in order to increase the pretilt angle of liquid crystal, Y ₁ is preferably a structure that has a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination thereof in the side chain. As such Y ₁ , formulas (Y-76) to (Y-97) are preferred. When the pretilt angle is to be increased, the proportion of the structure of Y ₁ is preferably 1 to 30 mol % of the entire Y ₁ , and further preferably 1 to 20 mol %. Furthermore, when a polyimide precursor or polyimide having a photoalignable side chain is used as the polymer of component (A), the polyimide precursor or polyimide has the following properties: The photoreactive side chain is preferred.

(式(c)中，R⁶ 表示-CH₂ -、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂ O-、-N(CH₃ )-、-CON(CH₃ )-或 -N(CH₃ )CO-。R⁷ 表示環狀、非取代或可被氟原子取代的碳數1~20的伸烷基(伸烷基的任意的-CH₂ -，可被-CF₂ -或 -CH＝CH-所取代，或可被以下所舉出之任一之基，以互不相鄰之方式來取代(作為該基為：-O-、-COO-、-OCO- 、-NHCO-、-CONH-、-NH-、碳環或雜環))。R⁸ 表示 -CH₂ -、-O-、-COO-、-OCO-、-NHCO-、-NH-、-N(CH₃ )- 、-CON(CH₃ )-、-N(CH₃ )CO-、碳環或雜環。R⁹ 表示乙烯基苯基、-CR¹⁰ ＝CH₂ 基、-CR¹⁰ (OH)-CH₃ 基、碳環、雜環或下述的式所表示的構造，R¹⁰ 表示可被氫原子或氟原子取代的甲基)。 (In formula (c), R ⁶ represents -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )- or -N(CH ₃ )CO-. R ⁷ represents a cyclic, unsubstituted or alkylene group having 1 to 20 carbon atoms that may be substituted by a fluorine atom (any alkylene group -CH ₂ - can be substituted by -CF ₂ - or -CH=CH-, or can be substituted by any of the groups listed below in a non-adjacent manner (the group is: - O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, carbocyclic or heterocyclic ring)). R ⁸ represents -CH ₂ -, -O-, -COO-, -OCO- , -NHCO-, -NH-, -N(CH ₃ )- , -CON(CH ₃ )-, -N(CH ₃ )CO-, carbocyclic or heterocyclic ring. ^{R 9} represents vinylphenyl, -CR ¹⁰ =CH ₂ group, -CR ¹⁰ (OH)-CH ₃ group, carbocyclic ring, heterocyclic ring or a structure represented by the following formula, R ¹⁰ represents a methyl group which may be substituted by a hydrogen atom or a fluorine atom).

製造上述的聚醯亞胺前驅物時，作為二胺，以使用上述式(c)所表示的側鏈經取代的二胺為便利。又，亦可使用在主鏈具有光配向性基的聚醯亞胺前驅物。此情形時，使用如下述式(2)所表示般的在胺與胺之間具有包含光配向性基的鍵結的二胺為便利。式(2)中，X¹ 為單鍵或碳數1~5的伸烷基，X² 為-OCO-CH＝CH-或-CH＝CH-COO-，X³ 為單鍵、碳數1~10的伸烷基或二價苯環，X⁴ 為單鍵、-OCO-CH＝CH-或-CH＝CH-COO-，X⁵ 為單鍵或碳數1~5的伸烷基。但具有1個以上的桂皮醯基。When producing the above-mentioned polyimide precursor, it is convenient to use a diamine with a side chain substituted represented by the above formula (c) as the diamine. In addition, a polyimide precursor having a photoalignment group in the main chain can also be used. In this case, it is convenient to use a diamine having a bond including a photo-alignment group between amines as represented by the following formula (2). In formula (2), X ¹ is a single bond or an alkylene group with 1 to 5 carbon atoms, X ² is -OCO-CH=CH- or -CH=CH-COO-, and X ³ is a single bond with 1 carbon number. ~10 alkylene group or divalent benzene ring, X ⁴ is a single bond, -OCO-CH=CH- or -CH=CH-COO-, X ⁵ is a single bond or an alkylene group with 1 to 5 carbon atoms. But it has more than 1 cinnamon base.

作為式(2)所表示的二胺，可舉出下述式(2-a)~(2-d)。式中，X為選自單鍵或醚(-O-)、酯(-COO-或OCO-)及醯胺(-CONH-或NHCO-)中的鍵結基，Y為單鍵或碳數1~5的伸烷基，Z為碳數1~10的伸烷基或伸苯基。苯環上的胺基的鍵結位置、或鍵結基相對於中央的苯環的位置並無特別限定。Examples of the diamine represented by formula (2) include the following formulas (2-a) to (2-d). In the formula, Alkylene group with 1 to 5 carbon atoms, and Z is an alkylene group or phenylene group with 1 to 10 carbon atoms. The bonding position of the amine group on the benzene ring or the position of the bonding group with respect to the central benzene ring is not particularly limited.

又，作為式(2)所表示的二胺的具體例，可舉出下述二胺。 Moreover, as a specific example of the diamine represented by formula (2), the following diamine can be mentioned.

使用含有以上述式(2)所表示的二胺來作為原料之本發明的聚醯胺酸、聚醯胺酸酯等的聚醯亞胺前驅物、聚醯亞胺或聚醯胺的液晶配向劑而形成的液晶配向膜，可降低因AC(交流)驅動所造成的液晶配向性能的變化(例如，液晶的配向方位的變化)。因此，具有該液晶配向膜的液晶顯示元件，在AC驅動下的液晶配向膜的液晶配向性能為穩定，因此不易產生因AC驅動所造成殘影。即，可發揮出因AC驅動所造成的殘影特性為非常地良好之類的效果。又，使用上述式(2)所表示的二胺而形成的液晶配向膜，其液晶配向性能本身亦為優異，能夠實現實質上未有配向缺陷的液晶配向膜。本發明中使用的聚醯亞胺前驅物係由二胺成分與四羧酸衍生物的反應而得到者，可舉出聚醯胺酸或聚醯胺酸酯等。Liquid crystal alignment using a polyamide precursor, a polyamide, or a polyamide of the present invention, such as a polyamide acid or a polyamide ester, containing a diamine represented by the above formula (2) as a raw material The liquid crystal alignment film formed by the agent can reduce changes in liquid crystal alignment performance (for example, changes in the alignment orientation of the liquid crystal) caused by AC (alternating current) driving. Therefore, in a liquid crystal display element having the liquid crystal alignment film, the liquid crystal alignment performance of the liquid crystal alignment film under AC driving is stable, and therefore image sticking caused by AC driving is less likely to occur. That is, it is possible to exhibit an effect that image sticking characteristics caused by AC driving are extremely good. In addition, the liquid crystal alignment film formed using the diamine represented by the above formula (2) has excellent liquid crystal alignment performance itself, and can realize a liquid crystal alignment film substantially free of alignment defects. The polyamide precursor used in the present invention is obtained by the reaction of a diamine component and a tetracarboxylic acid derivative, and examples thereof include polyamide acid, polyamide ester, and the like.

＜聚醯亞胺前驅物(聚醯胺酸)之製造＞作為被使用於本發明中的聚醯亞胺前驅物的聚醯胺酸，可藉由以下之方法來製造。具體而言係可藉由將四羧酸二酐與二胺，在有機溶劑的存在下以-20~150℃(較佳為0~50℃)中，以30分鐘~24小時(較佳為1~12小時)使其反應來合成。＜Manufacturing of polyimide precursor (polyamide acid)＞ The polyimide precursor used in the present invention can be produced by the following method. Specifically, it can be prepared by mixing tetracarboxylic dianhydride and diamine in the presence of an organic solvent at -20~150°C (preferably 0~50°C) for 30 minutes to 24 hours (preferably 1~12 hours) to react to synthesize.

二胺成分與四羧酸成分的反應，一般為在有機溶劑中來進行。作為此時使用的有機溶劑，只要是能溶解已生成的聚醯亞胺前驅物即可，並無特別限定。於下述舉出反應中使用的有機溶劑的具體例，但並非被限定於該等的例子。可舉出例如N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮或γ-丁內酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲亞碸或1,3-二甲基-咪唑啶酮。又，聚醯亞胺前驅物的溶解性為高時，可使用甲基乙基酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮或下述的式[D-1]~式[D-3]所表示的有機溶劑。式[D-1]中，D¹ 表示碳數1~3的烷基，式[D-2]中，D² 表示碳數1~3的烷基，式[D-3]中，D³ 表示碳數1~4的烷基。該等的有機溶劑係可單獨使用、亦可混合來使用。進而，即使是不會溶解聚醯亞胺前驅物的溶劑，在已生成的聚醯亞胺前驅物為不會析出的範圍內，亦可混合在前述溶劑中來使用。又，有機溶劑中之水分，因會阻礙聚合反應，進而成為使已生成的聚醯亞胺前驅物水解的原因，故有機溶劑係以使用已脫水乾燥者為較佳。The reaction between the diamine component and the tetracarboxylic acid component is generally carried out in an organic solvent. The organic solvent used at this time is not particularly limited as long as it can dissolve the generated polyimide precursor. Specific examples of the organic solvent used in the reaction are given below, but the solvent is not limited to these examples. Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethyl Acetamide, dimethyltrisoxide or 1,3-dimethyl-imidazolidinone. When the solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula can be used [ D-1]~organic solvent represented by formula [D-3]. In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms. In formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms. In formula [D-3], D ³ Represents an alkyl group with 1 to 4 carbon atoms. These organic solvents can be used individually or in mixture. Furthermore, even if it is a solvent that does not dissolve the polyimide precursor, it can be mixed with the solvent and used within the range that the generated polyimide precursor does not precipitate. In addition, the moisture in the organic solvent will hinder the polymerization reaction and further cause the hydrolysis of the generated polyimide precursor. Therefore, it is better to use an organic solvent that has been dehydrated and dried.

反應系中的聚醯胺酸聚合物的濃度，就不易引起聚合物的析出、且容易得到高分子量體之點而言，以1~30質量%為較佳，以5~20質量%為又較佳。The concentration of the polyamic acid polymer in the reaction system is preferably 1 to 30 mass %, and 5 to 20 mass % is preferable from the point of not easily causing precipitation of the polymer and easily obtaining a high molecular weight body. Better.

以上述般之方式所得到的聚醯胺酸係藉由一邊充分使反應溶液攪拌，一邊注入在不良溶劑中，從而可使聚合物析出並回收。又，進行多次析出，並利用不良溶劑洗淨後，藉由常溫或者加熱乾燥，從而可得到被純化的聚醯胺酸的粉末。不良溶劑並無特別限定，可舉出水、甲醇、乙醇、己烷、丁基賽路蘇、丙酮、甲苯等。The polyamide obtained in the above manner can be precipitated and recovered by injecting the reaction solution into a poor solvent while sufficiently stirring the reaction solution. Moreover, after precipitating multiple times and washing with a poor solvent, it is possible to obtain purified polyamide powder by drying at room temperature or heating. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butylserosol, acetone, toluene, and the like.

＜聚醯亞胺前驅物(聚醯胺酸酯)之製造＞作為被使用於本發明中的聚醯亞胺前驅物的聚醯胺酸酯，可依以下所表示的(1)、(2)或(3)的製法來製造。<Production of polyimide precursor (polyamic acid ester)> The polyamic acid ester used as the polyimide precursor in the present invention can be produced by the production method (1), (2) or (3) shown below.

(1)由聚醯胺酸來製造時聚醯胺酸酯係可藉由將如前述般所製造的聚醯胺酸進行酯化而來製造。具體而言可藉由將聚醯胺酸與酯化劑在有機溶劑的存在下，以-20~150℃，較佳為0~50℃中，以30分鐘~24小時，較佳為1~4小時使其反應而來製造。(1) When made of polyamide The polyamic acid ester system can be produced by esterifying the polyamic acid produced as described above. Specifically, the polyamide and the esterifying agent can be mixed in the presence of an organic solvent at -20~150°C, preferably 0~50°C, for 30 minutes to 24 hours, preferably 1~ Let it react for 4 hours to produce.

作為酯化劑係以藉由純化而可容易去除者為較佳，可舉出N,N-二甲基甲醯胺二甲基縮醛、N,N-二甲基甲醯胺二乙基縮醛、N,N-二甲基甲醯胺二丙基縮醛、N,N-二甲基甲醯胺二新戊基丁基縮醛、N,N-二甲基甲醯胺二-t-丁基縮醛、1-甲基-3-p-甲苯三氮烯、1-乙基-3-p-甲苯三氮烯、1-丙基-3-p-甲苯三氮烯、4-(4,6-二甲氧基-1,3,5-三嗪-2-基)-4-甲基嗎啉鎓氯化物等。酯化劑的添加量，相對於聚醯胺酸的重複單位1莫耳，以2~6莫耳當量為較佳。The esterifying agent is preferably one that can be easily removed by purification, and examples thereof include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide diethyl. Acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dineopentylbutyl acetal, N,N-dimethylformamide di- t-Butyl acetal, 1-methyl-3-p-toluenetriazene, 1-ethyl-3-p-toluenetriazene, 1-propyl-3-p-toluenetriazene, 4 -(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, etc. The amount of esterification agent added is preferably 2 to 6 molar equivalents relative to 1 mole of the repeating unit of polyamide acid.

作為有機溶劑，可舉出例如N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮或γ-丁內酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲亞碸或1,3-二甲基-咪唑啶酮。又，聚醯亞胺前驅物的溶劑溶解性為高時，可使用甲基乙基酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮或前述式[D-1]~式[D-3]所表示的有機溶劑。Examples of the organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N -Dimethylacetamide, dimethyltrisoxide or 1,3-dimethyl-imidazolidinone. In addition, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the aforementioned formula [D -1]~organic solvent represented by formula [D-3].

該等的有機溶劑係可單獨使用、亦可混合來使用。進而，即使是不會溶解聚醯亞胺前驅物的溶劑，在已生成的聚醯亞胺前驅物為不會析出的範圍內，亦可混合在前述溶劑中來使用。又，有機溶劑中之水分，因會阻礙聚合反應，進而成為使已生成的聚醯亞胺前驅物水解的原因，故有機溶劑係以使用已脫水乾燥者為較佳。上述的反應中使用的溶劑，就聚合物的溶解性而言，以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮或γ-丁內酯為較佳，該等係可混合1種或2種以上來使用。製造時的濃度，就不易引起聚合物的析出、且容易得到高分子量體之點而言，以1~30質量%為較佳，以5~20質量%為又較佳。These organic solvents can be used individually or in mixture. Furthermore, even if it is a solvent that does not dissolve the polyimide precursor, it can be mixed with the solvent and used within the range that the generated polyimide precursor does not precipitate. In addition, the moisture in the organic solvent will hinder the polymerization reaction and further cause the hydrolysis of the generated polyimide precursor. Therefore, it is better to use an organic solvent that has been dehydrated and dried. The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidinone or γ-butyrolactone in terms of polymer solubility. One type or two or more types can be mixed and used. The concentration during production is preferably 1 to 30 mass %, and 5 to 20 mass % is more preferably from the point where the polymer is unlikely to precipitate and a high molecular weight body is easily obtained.

(2)藉由四羧酸二酯二氯化物與二胺的反應來製造時聚醯胺酸酯係可由四羧酸二酯二氯化物(tetracarboxylic acid diester dichloride)與二胺來製造。具體而言可藉由將四羧酸二酯二氯化物與二胺，在鹼與有機溶劑的存在下，以-20~150℃，較佳為0~50℃中，以30分鐘~24小時，較佳為1~4小時使其反應來製造。(2) When produced by the reaction of tetracarboxylic acid diester dichloride and diamine Polyamide esters can be produced from tetracarboxylic acid diester dichloride and diamine. Specifically, it can be prepared by mixing tetracarboxylic acid diester dichloride and diamine in the presence of an alkali and an organic solvent at -20~150°C, preferably 0~50°C, for 30 minutes to 24 hours. , preferably 1 to 4 hours for the reaction to be produced.

作為前述鹼係可使用吡啶、三乙基胺、4-二甲基胺基吡啶等，但為了使反應穩定地進行，以吡啶為較佳。鹼的添加量，就容易去除的量、且容易得到高分子量體之點而言，相對於四羧酸二酯二氯化物，以2~4倍莫耳為較佳。Pyridine, triethylamine, 4-dimethylaminopyridine, etc. can be used as the aforementioned base. However, in order to make the reaction proceed stably, pyridine is preferred. The added amount of the base is preferably 2 to 4 moles relative to the tetracarboxylic acid diester dichloride in terms of an amount that is easily removed and a high molecular weight body is easily obtained.

作為前述有機溶劑，就單體及聚合物的溶解性而言，以N-甲基-2-吡咯啶酮或γ-丁內酯為較佳，該等亦可混合1種或2種以上來使用。製造時的聚合物濃度，就不易引起聚合物的析出、且容易得到高分子量體之點而言，以1~30質量%為較佳，以5~20質量%為又較佳。又，為了防止四羧酸二酯二氯化物的水解，故聚醯胺酸酯的製造中使用的有機溶劑以盡可能進行脫水者為較佳，在氮環境中，以防止外氣的混入者為較佳。As the aforementioned organic solvent, N-methyl-2-pyrrolidone or γ-butyrolactone is preferred in terms of solubility of monomers and polymers, and one or more of these may be mixed. use. The polymer concentration during production is preferably 1 to 30% by mass, and further preferably 5 to 20% by mass, so that precipitation of the polymer is less likely to occur and a high molecular weight body is easily obtained. In addition, in order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the organic solvent used in the production of the polyamide ester is preferably one that dehydrates as much as possible and is in a nitrogen environment to prevent the mixing of outside air. For better.

(3)由四羧酸二酯與二胺來製造時聚醯胺酸酯係可藉由四羧酸二酯與二胺進行縮聚合來製造。具體而言係可藉由將四羧酸二酯與二胺，在縮合劑、鹼、及有機溶劑的存在下，以0~150℃，較佳為0~100℃中，以30分鐘~24小時，較佳為3~15小時使其反應來製造。(3) When produced from tetracarboxylic acid diester and diamine Polyamic acid esters can be produced by condensation polymerization of tetracarboxylic acid diester and diamine. Specifically, it can be achieved by combining the tetracarboxylic acid diester and the diamine in the presence of a condensing agent, an alkali, and an organic solvent at 0 to 150°C, preferably 0 to 100°C, for 30 minutes to 24 hour, preferably 3 to 15 hours to react to produce it.

作為前述縮合劑係可使用三苯基亞磷酸酯、二環己基碳二亞胺、1-乙基-3-(3-二甲基胺基丙基)碳二亞胺鹽酸鹽、N,N’-羰基二咪唑、二甲氧基-1,3,5-三嗪基甲基嗎福林鎓、O-(苯并***-1-基)-N,N,N’,N’-四甲基脲四氟硼酸鹽、O-(苯并***-1-基)-N,N,N’,N’-四甲基脲六氟磷酸鹽、(2,3-二氫-2-硫酮基-3-苯并噁唑基)膦酸二苯基酯等。縮合劑的添加量，相對於四羧酸二酯，以2~3倍莫耳為較佳。As the aforementioned condensation agent system, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N' -Tetramethylurea tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylurea hexafluorophosphate, (2,3-dihydro- 2-Thionyl-3-benzoxazolyl)phosphonic acid diphenyl ester, etc. The amount of condensation agent added is preferably 2 to 3 times molar relative to the tetracarboxylic acid diester.

作為前述鹼，可使用吡啶、三乙基胺等的3級胺。鹼的添加量，就容易去除的量、且容易得到高分子量體之點而言，相對於二胺成分，以2~4倍莫耳為較佳。又，上述反應中，藉由加入路易斯酸來作為添加劑，可使反應有效率地進行。作為路易斯酸係以氯化鋰、溴化鋰等的鹵化鋰為較佳。路易斯酸的添加量，相對於二胺成分，以0~1.0倍莫耳為較佳。As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of alkali added is preferably 2 to 4 moles relative to the diamine component in terms of an amount that can be easily removed and a high molecular weight body can be easily obtained. Furthermore, in the above reaction, by adding a Lewis acid as an additive, the reaction can proceed efficiently. As the Lewis acid system, lithium halides such as lithium chloride and lithium bromide are preferred. The optimal amount of Lewis acid added is 0 to 1.0 molar relative to the diamine component.

上述3種的聚醯胺酸酯之製造方法中，為了得到高分子量的聚醯胺酸酯，故以上述(1)或(2)的製法為特佳。以上述般之方式所得到的聚醯胺酸酯的溶液係藉由一邊充分使其攪拌，一邊注入在不良溶劑中，從而可使聚合物析出。進行多次析出，並利用不良溶劑洗淨後，藉由常溫或者加熱乾燥，從而可得到被純化的聚醯胺酸酯的粉末。不良溶劑並無特別限定，可舉出水、甲醇、乙醇、己烷、丁基賽路蘇、丙酮、甲苯等。Among the above three methods for producing polyamic acid ester, in order to obtain a high molecular weight polyamic acid ester, the production method described above (1) or (2) is particularly preferred. The polyamic acid ester solution obtained in the above manner is poured into a poor solvent while being sufficiently stirred, so that the polymer can be precipitated. After multiple precipitations, washing with a poor solvent, and drying at room temperature or heating, the purified polyamic acid ester powder can be obtained. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butylserosol, acetone, toluene, and the like.

＜聚醯亞胺＞被使用於本發明中的聚醯亞胺((A)成分中的醯亞胺化聚合物)，可藉由將前述的聚醯胺酸酯或聚醯胺酸進行醯亞胺化來製造。＜Polyimide＞ The polyimide (the imidized polymer in component (A)) used in the present invention can be produced by imidizing the aforementioned polyamide ester or polyamic acid.

由聚醯胺酸來製造聚醯亞胺時，在以二胺成分與四羧酸二酐的反應而得到的前述聚醯胺酸的溶液中，添加觸媒來使其反應的化學性醯亞胺化為簡便。該化學性醯亞胺化係以相對低溫來進行醯亞胺化反應，因而在醯亞胺化的過程中不易引起聚合物的分子量降低，故為較佳。化學性醯亞胺化係可藉由如下述般來進行：將欲使其醯亞胺化的聚醯胺酸，在有機溶劑中，在鹼性觸媒與酸酐的存在下進行攪拌。作為有機溶劑，可使用前述的聚合反應時中使用的有機溶劑。作為鹼性觸媒，可舉出吡啶、三乙基胺、三甲基胺、三丁基胺、三辛基胺等。其中，吡啶係具有使反應進行的適度的鹼性，故為較佳。又，作為酸酐可舉出乙酸酐、偏苯三酸酐、焦蜜石酸二酐等，其中，若使用乙酸酐時，反應結束後的純化將變得容易，故為較佳。When producing polyimide from polyamide, a chemical imide that reacts by adding a catalyst to a solution of the polyamide obtained by reacting a diamine component and a tetracarboxylic dianhydride is added. Amination is easy. This chemical imidization is preferred because the imidization reaction is carried out at a relatively low temperature, so that the molecular weight of the polymer is not easily reduced during the imidization process. The chemical imidization system can be performed by stirring the polyamide to be imidized in an organic solvent in the presence of an alkaline catalyst and an acid anhydride. As the organic solvent, the organic solvent used in the aforementioned polymerization reaction can be used. Examples of the alkaline catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, the pyridine system is preferable since it has a moderate basicity that allows the reaction to proceed. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, pyromelite dianhydride, and the like. Among them, acetic anhydride is preferred because purification after completion of the reaction becomes easy.

進行上述醯亞胺化反應時的溫度為-20~140℃，較佳為0~100℃，反應時間可以0.5~100小時，較佳可以1~80小時來進行。鹼性觸媒的量為醯胺酸的0.5~30莫耳倍，較佳為2~20莫耳倍，酸酐的量為醯胺酸的1~50莫耳倍，較佳為3~30莫耳倍。所得到的聚合物的醯亞胺化率係可藉由調節觸媒量、溫度、反應時間來控制。The temperature when carrying out the above-mentioned imidization reaction is -20~140°C, preferably 0~100°C, and the reaction time can be 0.5~100 hours, preferably 1~80 hours. The amount of the alkaline catalyst is 0.5 to 30 mol times of the amide acid, preferably 2 to 20 mol times, and the amount of the acid anhydride is 1 to 50 mol times of the amide acid, preferably 3 to 30 mol times. Ear times. The imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.

聚醯胺酸酯或聚醯胺酸的醯亞胺化反應後的溶液中，因為殘留已添加的觸媒等，故藉由以下所述的手段來回收所得到的醯亞胺化聚合物，並利用有機溶劑進行再溶解後，作為本發明的液晶配向劑的(A)成分來使用為較佳。以上述般之方式所得到的聚醯亞胺的溶液係可藉由一邊充分攪拌，一邊注入在不良溶劑中，從而使聚合物析出。進行多次析出，並利用不良溶劑洗淨後，藉由常溫或者加熱乾燥，從而可得到被純化的聚醯亞胺的粉末。前述不良溶劑並無特別限定，可舉出甲醇、丙酮、己烷、丁基賽珞蘇、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯、苯等。Since the added catalyst, etc. remain in the solution after the imidization reaction of polyamide ester or polyamic acid, the obtained imidized polymer is recovered by the following means: After redissolving with an organic solvent, it is preferably used as component (A) of the liquid crystal alignment agent of the present invention. The solution of the polyimide obtained in the above manner can be poured into a poor solvent while being sufficiently stirred to precipitate the polymer. After multiple precipitations and washing with a poor solvent, the purified polyimide powder can be obtained by drying at room temperature or heating. The poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butylcellulose, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.

＜側鏈型丙烯酸聚合物＞作為本發明的(A)成分的樣態之一的側鏈型丙烯酸聚合物係在指定的溫度範圍內展現出液晶性並具有感光性。側鏈型丙烯酸聚合物，較佳以200~450nm的波長範圍的光來進行反應，且在100~300℃的溫度範圍內展現出液晶性者為佳。作為側鏈型丙烯酸聚合物，較佳為具有下述般的感光性側鏈：以較佳為200~450nm(又較佳為250~400nm)的波長範圍的光來進行反應的感光性側鏈。作為側鏈型丙烯酸聚合物，較佳為具有下述般的液晶基(mesogenic group)：用來在較佳為100~350℃(又較佳為120~300℃)的溫度範圍內展現出液晶性的液晶基。＜Side chain type acrylic polymer＞ The side chain acrylic polymer which is one aspect of the component (A) of the present invention exhibits liquid crystallinity in a specified temperature range and has photosensitivity. The side-chain acrylic polymer preferably reacts with light in the wavelength range of 200 to 450 nm and exhibits liquid crystallinity in the temperature range of 100 to 300°C. The side chain acrylic polymer preferably has photosensitive side chains that react with light in a wavelength range of preferably 200 to 450 nm (more preferably 250 to 400 nm). . The side-chain acrylic polymer preferably has a mesogenic group that exhibits liquid crystal in a temperature range of preferably 100 to 350°C (more preferably 120 to 300°C). Liquid crystal base.

側鏈型丙烯酸聚合物係鍵結了主鏈具有感光性的側鏈，故對光感應而可引起交聯反應、異構化反應、或光弗萊斯重排(Fries rearrangement)。具有感光性的側鏈的構造，係以對光感應而引起交聯反應、或光弗萊斯重排者為宜，以引起交聯反應者為更適宜。此時，即使是被暴露於熱等的外部應力下，亦可長時間穩定地保持所實現的配向控制能力。能夠展現出液晶性的感光性側鏈型丙烯酸聚合物膜的構造，只要是滿足這種特性即可，並無特別限定，但以側鏈構造具有剛硬的液晶基成分為較佳。此時，將該側鏈型丙烯酸聚合物製成液晶配向膜時，可得到穩定的液晶配向。Side-chain acrylic polymers are bonded with photosensitive side chains of the main chain, so they can cause cross-linking reactions, isomerization reactions, or photo-Fries rearrangement in response to light. The structure of the photosensitive side chain is preferably one that induces cross-linking reaction or photo-Frys rearrangement in response to light, and more preferably one that induces cross-linking reaction. In this case, the achieved alignment control capability can be stably maintained for a long time even if it is exposed to external stress such as heat. The structure of the photosensitive side chain type acrylic polymer film that can exhibit liquid crystallinity is not particularly limited as long as it satisfies this characteristic. However, it is preferable that the side chain structure has a rigid liquid crystal base component. At this time, when the side chain acrylic polymer is made into a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

作為側鏈型丙烯酸聚合物的構造，較佳為例如下述般的構造：具有主鏈與和該主鏈鍵結的側鏈，該側鏈具有聯苯基、三聯苯基、苯基環己基、苯基苯甲酸酯基、偶氮苯基等的液晶基成分，與鍵結於先端部的對光感應而進行交聯反應或異構化反應的感光性基的構造；或者，具有主鏈與和該主鏈鍵結的側鏈，該側鏈成為液晶基成分，且具有會進行光弗萊斯重排反應的苯基苯甲酸酯基的構造。The structure of the side chain acrylic polymer is preferably a structure having a main chain and a side chain bonded to the main chain, and the side chain has a biphenyl group, a terphenyl group, or a phenylcyclohexyl group. , a liquid crystal base component such as a phenyl benzoate group and an azophenyl group, and a photosensitive group bonded to the tip portion that reacts to light and undergoes a cross-linking reaction or isomerization reaction; or has a main structure chain and a side chain bonded to the main chain. The side chain becomes a liquid crystalline component and has a structure of a phenyl benzoate group that undergoes a photo-Fries rearrangement reaction.

作為側鏈型丙烯酸聚合物的構造的具體例，較佳為具有下述的主鏈與側鏈的構造：主鏈為源自於選自由烴、(甲基)丙烯酸酯、依康酸酯、富馬酸酯、馬來酸酯、α-亞甲基-γ-丁內酯、苯乙烯、乙烯基、馬來醯亞胺及降莰烯所成的群組中的至少1種的化合物的自由聚合性基，側鏈為由下述式(i)~(v)之至少1種所成。 As a specific example of the structure of the side chain type acrylic polymer, a structure having the following main chain and side chain is preferred: the main chain is derived from a hydrocarbon, (meth)acrylate, itaconate, At least one compound selected from the group consisting of fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide and norbornene The free polymerizable group and the side chain are composed of at least one of the following formulas (i) to (v).

式中，Ar₁ 表示從苯環、萘環、吡咯環、呋喃環、噻吩環或吡啶環之中去除2個氫原子而成的二價取代基。 Ar₂ 及Ar₃ 分別獨立為從苯環、萘環、吡咯環、呋喃環、噻吩環或吡啶環之中去除2個氫原子而成的二價取代基。q1與q2之一方為1，另一方為0。 Ar₄ 及Ar₅ 分別獨立表示從苯環、萘環、吡咯環、呋喃環、噻吩環或吡啶環之中去除2個氫原子而成的二價取代基。Y₁ -Y₂ 表示-CH＝CH-、-CH＝N-、-N＝CH-或-C≡C-。In the formula, Ar ₁ represents a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, naphthalene ring, pyrrole ring, furan ring, thiophene ring or pyridine ring. Ar ₂ and Ar ₃ are each independently a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, naphthalene ring, pyrrole ring, furan ring, thiophene ring or pyridine ring. One of q1 and q2 is 1, and the other is 0. Ar ₄ and Ar ₅ each independently represent a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, naphthalene ring, pyrrole ring, furan ring, thiophene ring or pyridine ring. Y ₁ -Y ₂ represents -CH=CH-, -CH=N-, -N=CH- or -C≡C-.

S₁ 、S₂ 及S₃ 分別獨立表示單鍵、碳數1~18的直鏈或分支狀的伸烷基、碳數5~8的伸環烷基、伸苯基或伸聯苯基，或表示選自單鍵、醚鍵、酯鍵、醯胺鍵、尿素鍵、胺基甲酸酯鍵、胺基鍵、羰基或此等的組合中的1種或2種以上的鍵結，或者表示介隔前述鍵結來將選自碳數1~18的直鏈或分支狀的伸烷基、碳數5~8的伸環烷基、伸苯基、伸聯苯基或此等的組合中的2以上10以下的部位予以連結而成的構造。尚，前述二價取代基亦可為下述的構造：介隔前述鍵結來將分別的複數個前述二價取代基予以連結而成的構造。S ₁ , S ₂ and S ₃ respectively independently represent a single bond, a linear or branched alkylene group with 1 to 18 carbon atoms, a cycloalkylene group with 5 to 8 carbon atoms, a phenyl group or a biphenyl group, or represents one or more types of bonds selected from single bonds, ether bonds, ester bonds, amide bonds, urea bonds, urethane bonds, amine bonds, carbonyl groups, or combinations thereof, or It means that a linear or branched alkylene group with a carbon number of 1 to 18, a cycloalkylene group with a carbon number of 5 to 8, a phenyl group, a biphenyl group, or a combination thereof is selected through the aforementioned bond. A structure in which 2 to 10 parts are connected together. Furthermore, the divalent substituent may have a structure in which a plurality of the divalent substituents are connected via the bond.

R₁₁ 表示氫原子、羥基、巰基、胺基、碳數1~10的烷基、碳數1~10的烷氧基、碳數1~8的烷基胺基或碳數2~16的二烷基胺基。前述苯環及/或萘環係可被選自鹵素原子、氰基、硝基、羧基及碳數2~11的烷氧基羰基中的相同或相異的1以上的基所取代。此時，碳數1~10的烷基可以是直鏈狀、分支或環狀，亦可以是組合此等的構造，亦可被鹵素原子所取代。R ₁₁ represents a hydrogen atom, a hydroxyl group, a mercapto group, an amine group, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkylamino group with 1 to 8 carbon atoms, or a diamine group with 2 to 16 carbon atoms. Alkylamino. The aforementioned benzene ring and/or naphthalene ring system may be substituted with at least one identical or different group selected from a halogen atom, a cyano group, a nitro group, a carboxyl group, and an alkoxycarbonyl group having 2 to 11 carbon atoms. In this case, the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, or may be a combination of these structures, or may be substituted by a halogen atom.

本發明的側鏈型丙烯酸聚合物係以含有液晶性側鏈為較佳。液晶性側鏈所具有的液晶基，可以是聯苯基或苯基苯甲酸酯等的單獨成為液晶基構造的基，亦可以是如苯甲酸等般的側鏈彼此進行氫鍵結而成為液晶基構造的基。作為側鏈所具有的液晶基係以下述的構造為較佳。 The side chain acrylic polymer of the present invention preferably contains liquid crystalline side chains. The liquid crystal group contained in the liquid crystal side chain may be a group that alone forms a liquid crystal structure such as a biphenyl group or phenyl benzoate, or may be a group formed by hydrogen bonding between side chains such as benzoic acid. Liquid crystal base structure. The liquid crystal group contained as a side chain preferably has the following structure.

＜側鏈型丙烯酸聚合物＞本發明的側鏈型丙烯酸聚合物，可藉由具有上述的感光性側鏈的光反應性側鏈單體及液晶性側鏈單體進行聚合而來得到。 [光反應性側鏈單體] 所謂光反應性側鏈單體，係指該單體在形成高分子時，可形成高分子的側鏈部位具有感光性側鏈的高分子。作為側鏈所具有的光反應性基係以上述式(i)~(v)所表示的構造為較佳。光反應性側鏈單體的更具體的例子，較佳為具有選自由烴、(甲基)丙烯酸酯、依康酸酯、富馬酸酯、馬來酸酯、α-亞甲基-γ-丁內酯、苯乙烯、乙烯基、馬來醯亞胺及降莰烯所成的群組中的至少1種化合物的自由聚合性基，及選自由上述式(i)~(v)所成的群組中的至少1種所成的感光性側鏈而成的構造。＜Side chain type acrylic polymer＞ The side chain acrylic polymer of the present invention can be obtained by polymerizing a photoreactive side chain monomer and a liquid crystalline side chain monomer having the above-mentioned photosensitive side chain. [Photoreactive side chain monomer] The so-called photoreactive side chain monomer means that when the monomer forms a polymer, the side chain portion of the polymer can form a polymer with photosensitive side chains. The photoreactive group contained as a side chain is preferably a structure represented by the above formulas (i) to (v). More specific examples of the photoreactive side chain monomer are preferably those selected from the group consisting of hydrocarbons, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ - A free polymerizable group of at least one compound in the group consisting of butyrolactone, styrene, vinyl, maleimide and norbornene, and is selected from the group consisting of the above formulas (i) to (v) A structure composed of at least one photosensitive side chain in the group.

[液晶性側鏈單體] 所謂液晶性側鏈單體係指源自該單體的高分子為展現出液晶性，且該高分子可在側鏈部位形成液晶基的單體。液晶性側鏈單體的更具體的例子，較佳為具有選自由烴、(甲基)丙烯酸酯、依康酸酯、富馬酸酯、馬來酸酯、α-亞甲基-γ-丁內酯、苯乙烯、乙烯基、馬來醯亞胺及降莰烯所成的群組中的至少1種化合物的自由聚合性基，及具有選自由前述的液晶基所成的群組中的至少1種的液晶性側鏈而成的構造。[Liquid crystalline side chain monomer] The so-called liquid crystalline side chain monomer refers to a monomer in which the polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a liquid crystal group at the side chain site. More specific examples of the liquid crystalline side chain monomer are preferably those selected from the group consisting of hydrocarbons, (meth)acrylic acid esters, itaconic acid esters, fumaric acid esters, maleic acid esters, and α-methylene-γ- A free polymerizable group of at least one compound from the group consisting of butyrolactone, styrene, vinyl, maleimide and norbornene, and a group having a liquid crystal group selected from the above A structure composed of at least one kind of liquid crystalline side chain.

本發明的側鏈型丙烯酸聚合物，可藉由上述展現出液晶性的光反應性側鏈單體之聚合反應來得到。又，亦可藉由未展現出液晶性的光反應性側鏈單體與液晶性側鏈單體的共聚合、或展現出液晶性的光反應性側鏈單體與液晶性側鏈單體的共聚合來得到。進而，在不損及液晶性之展現能力的範圍內，可與其他的單體共聚合。The side chain acrylic polymer of the present invention can be obtained by the polymerization reaction of the photoreactive side chain monomer exhibiting liquid crystallinity. Alternatively, a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer may be copolymerized, or a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer may be copolymerized. obtained by copolymerization. Furthermore, it can be copolymerized with other monomers within the range that the ability to express liquid crystallinity is not impaired.

作為其他的單體，可舉出例如可工業上取得的能夠進行自由聚合反應的單體。作為其他的單體之具體例，可舉出不飽和羧酸、丙烯酸酯、甲基丙烯酸酯、馬來醯亞胺、丙烯腈、馬來酸酐、苯乙烯化合物、乙烯基化合物等。Examples of other monomers include industrially available monomers capable of free polymerization. Specific examples of other monomers include unsaturated carboxylic acid, acrylate, methacrylate, maleimide, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like.

作為不飽和羧酸之具體例，可舉出丙烯酸、甲基丙烯酸、伊康酸、馬來酸、福馬酸等。作為丙烯酸酯，可舉出例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸異丙酯、丙烯酸苄酯、丙烯酸萘酯、丙烯酸蒽基酯、丙烯酸蒽基甲酯、丙烯酸苯基酯、丙烯酸2,2,2-三氟乙酯、丙烯酸tert-丁酯、丙烯酸環己酯、丙烯酸異莰基酯、丙烯酸2-甲氧基乙酯、丙烯酸甲氧基三乙二醇酯、丙烯酸2-乙氧基乙酯、丙烯酸四氫糠酯、丙烯酸3-甲氧基丁酯、丙烯酸2-甲基-2-金剛烷基酯、丙烯酸2-丙基-2-金剛烷基酯、丙烯酸8-甲基-8-三環癸酯、丙烯酸8-乙基-8-三環癸酯等。Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid. Examples of acrylic esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthracenyl methyl acrylate, phenyl acrylate, and 2,2 acrylate. 2-Trifluoroethyl, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate Ester, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8 acrylate -Tricyclodecyl ester, 8-ethyl-8-tricyclodecyl acrylate, etc.

作為甲基丙烯酸酯，可舉出例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異丙酯、甲基丙烯酸苄基酯、甲基丙烯酸萘基酯、甲基丙烯酸蒽基酯、甲基丙烯酸蒽基甲酯、甲基丙烯酸苯基酯、甲基丙烯酸2,2,2-三氟乙酯、甲基丙烯酸tert-丁酯、甲基丙烯酸環己酯、甲基丙烯酸異莰基酯、甲基丙烯酸2-甲氧基乙酯、甲基丙烯酸甲氧基三乙二醇酯、甲基丙烯酸2-乙氧基乙酯、甲基丙烯酸四氫糠酯、甲基丙烯酸3-甲氧基丁酯、甲基丙烯酸2-甲基-2-金剛烷基酯、甲基丙烯酸2-丙基-2--金剛烷基酯、甲基丙烯酸8-甲基-8-三環癸酯、及甲基丙烯酸8-乙基-8-三環癸酯等。進而，亦可使用(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸(3-甲基-3-氧雜環丁烷基)甲酯、(甲基)丙烯酸(3-乙基-3-氧雜環丁烷基)甲酯等的具有環狀醚基的(甲基)丙烯酸酯化合物。Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, and anthryl methacrylate. Anthracenyl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate Ester, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methyl methacrylate Oxybutyl ester, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate , and 8-ethyl-8-tricyclodecyl methacrylate, etc. Furthermore, glycidyl (meth)acrylate, (meth)acrylic acid (3-methyl-3-oxetanyl)methyl ester, (meth)acrylic acid (3-ethyl-3- A (meth)acrylate compound having a cyclic ether group such as oxetanyl)methyl ester.

作為乙烯基化合物，可舉出例如乙烯基醚、甲基乙烯基醚、苄基乙烯基醚、2-羥基乙基乙烯基醚、苯基乙烯基醚、丙基乙烯基醚等。作為苯乙烯化合物，可舉出例如苯乙烯、甲基苯乙烯、氯苯乙烯、溴苯乙烯等。作為馬來醯亞胺化合物，可舉出例如馬來醯亞胺、N-甲基馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等。Examples of vinyl compounds include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, and the like. Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like. Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

本發明的側鏈型丙烯酸聚合物的製造方法並不被特別限定，可利用工業上使用的通用方法。具體而言係可藉由利用液晶性側鏈單體或光反應性側鏈單體的乙烯基之陽離子聚合、自由聚合、陰離子聚合等而來製造。該等之中，就反應控制的難易度等的觀點而言，以自由聚合為特佳。The production method of the side chain type acrylic polymer of the present invention is not particularly limited, and a general method used in industry can be used. Specifically, it can be produced by cationic polymerization, free polymerization, anionic polymerization, etc. of a vinyl group using a liquid crystalline side chain monomer or a photoreactive side chain monomer. Among these, free polymerization is particularly preferred from the viewpoint of ease of reaction control and the like.

自由聚合的聚合起始劑係可使用AIBN(偶氮雙異丁腈)等的周知自由聚合起始劑、或可逆性加成-裂解型連鏈移動(RAFT)聚合試劑等的周知化合物。自由聚合法並無特別限制，可使用乳化聚合法、懸濁聚合法、分散聚合法、沉澱聚合法、塊狀聚合法、溶液聚合法等。As the polymerization initiator for free polymerization, known free polymerization initiators such as AIBN (azobisisobutyronitrile) or well-known compounds such as reversible addition-fragmentation chain transfer (RAFT) polymerization reagents can be used. The free polymerization method is not particularly limited, and emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, block polymerization, solution polymerization, etc. can be used.

作為前述側鏈型丙烯酸聚合物的聚合反應中使用的有機溶劑，只要是生成的聚合物為溶解者即可，並無特別限定。以下可舉出其具體例。 N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-甲基己內醯胺、二甲亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、異丙基醇、甲氧基甲基戊醇、二戊烯、乙基戊基酮、甲基壬基酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、甲基賽珞蘇、乙基賽珞蘇、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丁基卡必醇、乙基卡必醇、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、倍異丁烯、乙酸戊酯、丁酸丁酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二己基醚、二噁烷、四氫呋喃、n-己烷、n-戊烷、n-辛烷、二乙基醚、環己酮、碳酸伸乙酯、碳酸伸丙酯、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、二甘醇二甲醚、4-羥基-4-甲基-2-戊酮、3-甲氧基-N,N-二甲基丙醯胺、3-乙氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺等。The organic solvent used in the polymerization reaction of the side chain type acrylic polymer is not particularly limited as long as the produced polymer is dissolved. Specific examples are given below. N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylhexanolide Amide, dimethylsterine, tetramethylurea, pyridine, dimethylsterine, hexamethylsterine, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylene Amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentyl ketone, methyl isopropyl ketone, methyl cellosol, ethyl cellosolve acetic acid Ester, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol di Methyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono Acetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethanol Isobutyl ether, isobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, tetrahydrofuran, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl carbonate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n acetate -Butyl ester, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, 3-methoxypropionic acid Ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, diglyme, 4-hydroxy- 4-Methyl-2-pentanone, 3-methoxy-N,N-dimethylpropylamide, 3-ethoxy-N,N-dimethylpropylamide, 3-butoxy- N,N-dimethylpropylamine, etc.

該等有機溶劑係可單獨使用、亦可混合來使用。進而，即使是不使生成的高分子溶解的溶劑，在生成的高分子不會析出的範圍內，亦可與上述的有機溶劑混合來使用。又，自由聚合中，有機溶劑中之氧氣係因成為阻礙聚合反應的原因，故有機溶劑係以使用盡可能脫氣者為較佳。自由聚合時的聚合溫度係可在30~150℃之任意的溫度來做選擇，較佳為50~100℃的範圍。These organic solvents can be used individually or in mixture. Furthermore, even a solvent that does not dissolve the produced polymer can be mixed with the above-mentioned organic solvent and used as long as the produced polymer does not precipitate. In addition, in free polymerization, oxygen in the organic solvent hinders the polymerization reaction, so it is preferable to use an organic solvent that is degassed as much as possible. The polymerization temperature during free polymerization can be selected at any temperature from 30 to 150°C, and is preferably in the range of 50 to 100°C.

又，反應係可在任意的濃度來進行，但濃度過低時則變得難以得到高分子量的聚合物，若濃度過高時，則反應液黏性變得過高而使得均勻的攪拌變得困難，因此單體濃度較佳為1~50質量%，又較佳為5~30質量%。反應初期在高濃度來進行，之後，以追加有機溶劑為較佳。上述自由聚合反應中，自由聚合起始劑的比率相對於單體為多時則所得到的高分子的分子量變小，若少時則所得到的高分子的分子量則變大，因此自由聚合起始劑的比率係相對於聚合的單體，較佳為0.05~15莫耳%，又較佳為0.1~10莫耳%。又，聚合時亦可追加各種單體成分、有機溶劑、自由聚合起始劑等。In addition, the reaction system can be carried out at any concentration. However, if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. It is difficult, so the monomer concentration is preferably 1 to 50 mass%, and more preferably 5 to 30 mass%. It is preferable to carry out the reaction at a high concentration in the initial stage, and then add an organic solvent. In the above free polymerization reaction, when the ratio of the free polymerization initiator to the monomer is large, the molecular weight of the polymer obtained becomes small, and when it is small, the molecular weight of the polymer obtained becomes large, so the free polymerization starts. The ratio of the starting agent relative to the polymerized monomer is preferably 0.05 to 15 mol%, and more preferably 0.1 to 10 mol%. In addition, various monomer components, organic solvents, free polymerization initiators, etc. may be added during polymerization.

從藉由上述聚合反應所得到的含有側鏈型丙烯酸聚合物的反應溶液回收生成的聚合物時，以將反應溶液投入在不良溶劑中，使已生成的聚合物沉澱為較佳。作為沉澱時使用的不良溶劑，可舉出甲醇、丙酮、己烷、庚烷、丁基賽珞蘇、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯、苯、二乙基醚、甲基乙基醚、水等。投入在不良溶劑中並使其沉澱的聚合物係以進行過濾並回收後，以在常壓或者減壓下，以常溫或者加熱來進行乾燥為較佳。又，沉澱回收的聚合物再溶解於有機溶劑中，重複再沉澱並回收的操作2~10次時，可使聚合物中之雜質減少。作為再沉澱時的不良溶劑，可舉出例如醇類、酮類、醚類、烴等，若使用選自該等之中的3種類以上的不良溶劑時，更進一步提升純化的效率，因此為較佳。When recovering the polymer produced from the reaction solution containing the side chain acrylic polymer obtained by the above polymerization reaction, it is preferable to put the reaction solution into a poor solvent to precipitate the produced polymer. Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butylcellulose, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, dibenzoic acid Ethyl ether, methyl ethyl ether, water, etc. The polymer system put into a poor solvent and precipitated is preferably filtered and recovered, and then dried under normal pressure or reduced pressure, at normal temperature or with heating. In addition, when the polymer recovered by precipitation is redissolved in an organic solvent, and the operation of reprecipitation and recovery is repeated 2 to 10 times, the impurities in the polymer can be reduced. Examples of poor solvents during reprecipitation include alcohols, ketones, ethers, hydrocarbons, etc. If three or more types of poor solvents selected from these are used, the purification efficiency will be further improved, so it is Better.

本發明的側鏈型丙烯酸聚合物的分子量，若考慮所得到的塗膜的強度、塗膜形成時的作業性、及塗膜的均勻性時，以GPC(Gel Permeation Chromatography)法所測定的重量平均分子量，以2,000~500,000為較佳，又較佳為5,000~100,000。本發明的液晶配向劑中的(A)成分之聚合物的含有量，可依欲形成之塗膜的厚度設定來作適當變更，但就形成均勻且無缺陷的塗膜之觀點而言，以1重量%以上為較佳，就溶液的保存穩定性之觀點而言，以10重量%以下為較佳，其中以3~7重量%為較佳。The molecular weight of the side chain acrylic polymer of the present invention is the weight measured by the GPC (Gel Permeation Chromatography) method when the strength of the coating film obtained, the workability during coating film formation, and the uniformity of the coating film are taken into consideration. The average molecular weight is preferably 2,000 to 500,000, and more preferably 5,000 to 100,000. The content of the polymer of component (A) in the liquid crystal alignment agent of the present invention can be appropriately changed according to the thickness setting of the coating film to be formed. However, from the perspective of forming a uniform and defect-free coating film, 1% by weight or more is preferred, and from the viewpoint of the storage stability of the solution, 10% by weight or less is preferred, and 3 to 7% by weight is particularly preferred.

＜(B)成分＞本發明的液晶配向劑中所含有的(B)成分為下述式(1)所表示的化合物。 (式中，Q¹ 及Q² 為選自下述式(Q1-1)及單鍵中的1種，Q¹ 及Q² 的至少1個為式(Q1-1)，q1及q2分別獨立為0或1，R² 及R³ 分別獨立為具有環氧部位的基及氫原子中的任一者，R² 及R³ 的至少1個為具有環氧部位的基) (式(Q1-1)中，R¹ 為氫原子或一價有機基。R¹ 的一價有機基，又較佳為甲基、苯基、具有環氧部位的基或熱分解性脫離基。<(B) component> The (B) component contained in the liquid crystal alignment agent of the present invention is a compound represented by the following formula (1). (In the formula, Q ¹ and Q ² are one selected from the following formula (Q1-1) and single bonds, at least one of Q ¹ and Q ² is the formula (Q1-1), q1 and q2 are independent is 0 or 1, R ² and R ³ are independently any one of a group having an epoxy site and a hydrogen atom, and at least one of R ² and R ³ is a group having an epoxy site) (In the formula (Q1-1), R ¹ is a hydrogen atom or a monovalent organic group. The monovalent organic group of R ¹ is preferably a methyl group, a phenyl group, a group having an epoxy site, or a thermally decomposable leaving group. .

所謂熱分解性脫離基係指藉由加熱來進行脫離並被取代成氫原子的取代基。上述熱分解性脫離基係胺基的保護基，只要是藉由熱被取代成氫原子的官能基即可，該構造並無特別限定。就液晶配向劑的保存穩定性之觀點而言，該保護基D係以在室溫中不會脫離為佳，較佳為以80℃以上的熱來進行脫離的保護基，更佳為以100℃以上的熱來進行脫離的保護基。就進行脫離的溫度之觀點而言，D係以tert-丁氧基羰基、或9-茀基甲氧基羰基為特佳。The thermally decomposable leaving group refers to a substituent that is removed by heating and replaced with a hydrogen atom. The protecting group for the thermally decomposable leaving group-based amine group is not particularly limited as long as it is a functional group that is substituted with a hydrogen atom by heat. From the perspective of the storage stability of the liquid crystal alignment agent, the protective group D is preferably one that does not detach at room temperature, preferably a protective group that detaches with heat of 80°C or above, and more preferably 100 The protective group is detached by heat above ℃. From the viewpoint of the detachment temperature, D is particularly preferably a tert-butoxycarbonyl group or a 9-benzomethoxycarbonyl group.

作為R¹ 、R² 及R³ 的定義中的具有環氧部位的基，可舉出縮水甘油基、3,4-環氧環己基等，就合成的難易度而言，以縮水甘油基為較佳。Examples of the group having an epoxy moiety in the definition of R ¹ , R ² and R ³ include glycidyl group, 3,4-epoxycyclohexyl group, etc. In terms of ease of synthesis, glycidyl group is Better.

作為(B)成分所表示的化合物的較佳的例子，可舉出例如下述(B-1)至(B-6)的化合物。 (B-1)：上述式(1)中，q1及q2為0，Q¹ 為(Q1-1)，R² 及R³ 為具有環氧基的基而成的化合物； (B-2)：上述式(1)中，q1及q2為0，Q¹ 為(Q1-1)，R² 為氫原子，R³ 為具有環氧基的基而成的化合物； (B-3)：上述式(1)中，q1及q2為1，Q¹ 為單鍵或(Q1-1)，Q² 為(Q1-1)，R² 及R³ 為具有環氧基的基而成的化合物； (B-4)：上述式(1)中，q1及q2為1，Q¹ 為單鍵或(Q1-1)，Q² 為(Q1-1)，R² 為氫原子，R³ 為具有環氧基的基而成的化合物； (B-5)：上述式(1)中，q1及q2為1，Q¹ 為(Q1-1)，Q² 為單鍵，R² 及R³ 為具有環氧基的基而成的化合物； (B-6)：上述式(1)中，q1及q2為1，Q¹ 為(Q1-1)，Q² 為單鍵，R² 為氫原子，R³ 為具有環氧基的基而成的化合物。Preferable examples of the compound represented by component (B) include the following compounds (B-1) to (B-6). (B-1): In the above formula (1), q1 and q2 are 0, Q ¹ is (Q1-1), and R ² and R ³ are compounds having an epoxy group; (B-2) : In the above formula (1), q1 and q2 are 0, Q ¹ is (Q1-1), R ² is a hydrogen atom, and R ³ is a compound having an epoxy group; (B-3): The above In formula (1), q1 and q2 are 1, Q ¹ is a single bond or (Q1-1), Q ² is (Q1-1), and R ² and R ³ are compounds having an epoxy group; (B-4): In the above formula (1), q1 and q2 are 1, Q ¹ is a single bond or (Q1-1), Q ² is (Q1-1), R ² is a hydrogen atom, and R ³ is a Compounds composed of epoxy groups; (B-5): In the above formula (1), q1 and q2 are 1, Q ¹ is (Q1-1), Q ² is a single bond, R ² and R ³ are Compounds having an epoxy group; (B-6): In the above formula (1), q1 and q2 are 1, Q ¹ is (Q1-1), Q ² is a single bond, and R ² is a hydrogen atom , R ³ is a compound having an epoxy group.

上述之中，作為較佳的(B)成分，可舉出例如由下述式B-1-1~式B-5-1中任意所表示的化合物。 Among the above, preferred examples of the component (B) include compounds represented by any of the following formulas B-1-1 to B-5-1.

上述(B)成分的化合物係使環氧鹵丙烷(epihalohydrin)與下述式(0)所表示的二胺反應後，藉由將所得到的加成反應物利用鹼處理來使其環化反應而可得到。 The compound of component (B) is prepared by reacting epihalohydrin with a diamine represented by the following formula (0), and then treating the resulting addition reaction product with an alkali to cyclize it. And available.

作為式(0)所表示的二胺亦可使用周知種類。As the diamine represented by formula (0), well-known types can also be used.

為了製造式(1)中R² 及R³ 的兩方為具有環氧部位的基之化合物時，相對於式(0)所表示的二胺，使用4當量以上的環氧鹵丙烷，較佳為使用8當量以上，之後再以鹼來進行處理即可。但，為了製造R¹ 亦為具有環氧部位的基之化合物時，則大量使用該環氧鹵丙烷即可。欲製造R² 及R³ 的一方為具有環氧部位的基，另一方為氫原子之化合物時，相對於式(0)所表示的二胺，使用2~2.2當量的環氧鹵丙烷，之後再以鹼來進行處理即可。In order to produce a compound in which both R ² and R ³ in the formula (1) are groups having an epoxy moiety, it is preferable to use 4 equivalents or more of epihalohydrin relative to the diamine represented by the formula (0). In order to use more than 8 equivalents, it can be treated with alkali afterwards. However, in order to produce a compound in which R ¹ is also a group having an epoxy moiety, a large amount of the epihalohydrin may be used. To produce a compound in which one of R ² and R ³ is a group having an epoxy moiety and the other is a hydrogen atom, use 2 to 2.2 equivalents of epihalohydrin relative to the diamine represented by formula (0), and then Then treat it with alkali.

(B)成分若過多時，會對液晶配向性帶來影響，若過少時，則無法充分得到本發明的效果。因此，液晶配向劑中的(B)成分的含有量，相對於(A)成分(100質量%)，以0.1~20質量%為較佳，以1~10質量%為又較佳。If the component (B) is too small, the liquid crystal alignment properties will be affected. If the component is too small, the effects of the present invention will not be fully obtained. Therefore, the content of component (B) in the liquid crystal alignment agent is preferably 0.1 to 20 mass % relative to component (A) (100 mass %), and more preferably 1 to 10 mass %.

＜液晶配向劑＞被使用於本發明中的液晶配向劑係具有選自由前述的(A)成分的聚醯亞胺前驅物及該聚醯亞胺前驅物的醯亞胺化聚合物所成的群組中的至少1種的聚合物(以下，稱為特定構造聚合物)及(B)成分的化合物被溶解在有機溶劑中的溶液之形態。特定構造聚合物的分子量係以重量平均分子量2,000~500,000為較佳，又較佳為5,000~300,000，更佳為10,000~100,000。又，數平均分子量係較佳為1,000~250,000，又較佳為2,500~150,000，更佳為5,000~50,000。＜Liquid crystal alignment agent＞ The liquid crystal alignment agent used in the present invention has at least one selected from the group consisting of the polyimide precursor of the aforementioned component (A) and the imidized polymer of the polyimide precursor. A form of a solution in which one type of polymer (hereinafter referred to as a specific structure polymer) and the compound of component (B) are dissolved in an organic solvent. The molecular weight of the polymer with a specific structure is preferably a weight average molecular weight of 2,000 to 500,000, more preferably 5,000 to 300,000, and more preferably 10,000 to 100,000. Moreover, the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and more preferably 5,000 to 50,000.

被使用於本發明中的液晶配向劑之聚合物的濃度，可依欲形成之塗膜的厚度設定來做適當變更，但就形成均勻且無缺陷的塗膜之觀點而言，以1重量%以上為較佳，就溶液的保存穩定性之觀點而言，以設為10重量%以下為較佳。被使用於本發明中的液晶配向劑所含有的有機溶劑(良溶劑)，只要是特定構造聚合物能均勻地溶解即可，並無特別限定。可舉出例如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、二甲亞碸、γ-丁內酯、1,3-二甲基-咪唑啶酮、甲基乙基酮、環己酮、環戊酮或4-羥基-4-甲基-2-戊酮等。其中，以使用N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、γ-丁內酯為較佳。進而，本發明的聚合物對溶劑的溶解性為高時，以使用前述式[D-1]~式[D-3]所表示的溶劑為較佳。本發明的液晶配向劑中的良溶劑係以液晶配向劑中所包含的溶劑整體的20~99質量%為佳。其中，以20~90質量%為較佳。又較佳為30~80質量%。The concentration of the polymer used in the liquid crystal alignment agent of the present invention can be appropriately changed according to the thickness of the coating film to be formed, but from the perspective of forming a uniform and defect-free coating film, 1% by weight The above is preferable, and from the viewpoint of the storage stability of the solution, it is preferably 10% by weight or less. The organic solvent (good solvent) contained in the liquid crystal alignment agent used in the present invention is not particularly limited as long as the polymer with a specific structure can be uniformly dissolved. Examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl Trisene, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone, etc. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferably used. Furthermore, when the solubility of the polymer of the present invention in a solvent is high, it is preferable to use the solvent represented by the aforementioned formula [D-1] to formula [D-3]. The good solvent in the liquid crystal alignment agent of the present invention is preferably 20 to 99 mass % of the total solvent contained in the liquid crystal alignment agent. Among them, 20 to 90 mass % is preferred. More preferably, it is 30~80 mass %.

本發明的液晶配向劑中，可使用用來提升塗佈液晶配向劑時的液晶配向膜的塗膜性或表面平滑性的溶劑(亦稱為不良溶劑)。以下為舉出不良溶劑的具體例，但並非被限定於該等的例子中。可舉出例如乙醇、異丙基醇、1-丁醇、2-丁醇、異丁基醇、tert-丁基醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊基醇、tert-戊基醇、3-甲基-2-丁醇、新戊基醇、1-己醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己醇、1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、2-甲基-2,4-戊二醇、2-乙基-1,3-己二醇、二丙基醚、二丁基醚、二己基醚、二噁烷、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚、1,2-丁氧基乙烷、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚、二乙二醇二丁基醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、3-乙氧基丁基乙酸酯、1-甲基戊基乙酸酯、2-乙基丁基乙酸酯、2-乙基己基乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、碳酸伸丙酯、碳酸伸乙酯、2-(甲氧基甲氧基)乙醇、乙二醇單丁基醚、乙二醇單異戊基醚、乙二醇單己基醚、2-(己氧基)乙醇、糠醇、二乙二醇、丙二醇、丙二醇單丁基醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲基醚乙酸酯、二丙二醇、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇二甲基醚、三丙二醇單甲基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、2-(2-乙氧基乙氧基)乙基乙酸酯、二乙二醇乙酸酯、三乙二醇、三乙二醇單甲基醚、三乙二醇單乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、乳酸甲基酯、乳酸乙基酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊基酯或前述式[D-1]~式[D-3]所表示的溶劑等。其中，以使用1-己醇、環己醇、1,2-乙二醇、1,2-丙二醇、丙二醇單丁基醚、乙二醇單丁基醚或二丙二醇二甲基醚為較佳。該等不良溶劑係以液晶配向劑中所包含的溶劑整體的1~80質量%為佳。其中，以10~80質量%為較佳。又較佳為20~70質量%。In the liquid crystal alignment agent of the present invention, a solvent (also called a poor solvent) used to improve the coating properties or surface smoothness of the liquid crystal alignment film when coating the liquid crystal alignment agent can be used. The following are specific examples of poor solvents, but are not limited to these examples. Examples include ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, and 2-methyl alcohol. 1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2- Methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1- Hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol , 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4- Pentylene glycol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether , Ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol Alcohol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetic acid Esters, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propyl carbonate, ethyl carbonate, 2-( Methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, furfuryl alcohol, diethylene glycol, propylene glycol , propylene glycol monobutyl ether, 1-(butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate , Ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate , diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid n -Butyl ester, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, 3-methoxypropionic acid Ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate, or solvents represented by the aforementioned formulas [D-1] to formulas [D-3], etc. Among them, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferred. . The amount of these poor solvents is preferably 1 to 80% by mass of the total solvent contained in the liquid crystal alignment agent. Among them, 10 to 80% by mass is preferred. More preferably, it is 20-70 mass %.

本發明的液晶配向劑，除了上述以外，亦可添加：本發明所記載的聚合物以外之聚合物；使液晶配向膜的介電率或導電性等的電特性變化為目的之介電質或者導電物質；使液晶配向膜與基板的密著性提升為目的之矽烷偶合劑；製成液晶配向膜時以提高膜的硬度或緻密度為目的之交聯性化合物；及進而，使聚醯亞胺前驅物在燒成塗膜時能效率良好地藉由加熱來進行醯亞胺化為目的之醯亞胺化促進劑等。In addition to the above, the liquid crystal alignment agent of the present invention may also add: polymers other than the polymers described in the present invention; dielectric substances for the purpose of changing electrical properties such as dielectric constant or conductivity of the liquid crystal alignment film; or Conductive substances; silane coupling agents for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate; cross-linking compounds for the purpose of improving the hardness or density of the film when making the liquid crystal alignment film; and further, making the polyethylene The amine precursor is an imidization accelerator for the purpose of efficiently performing imidization by heating when the coating film is fired.

＜液晶配向膜＞本發明的液晶配向膜係將上述液晶配向劑塗佈在基板上，並進行乾燥、燒成後所得到的膜。作為塗佈本發明的液晶配向劑的基板，只要是具有高透明性的基板即可，並無特別限定，可使用玻璃基板、氮化矽基板、丙烯酸基板、聚碳酸酯基板等的塑膠基板等，以使用形成有用來驅動液晶的ITO電極的基板，就製程的簡單化之觀點而言為較佳。又，反射型的液晶顯示元件因僅於單側的基板，故亦可使用矽晶圓等的不透明的物質，此時電極亦可使用鋁等的可反射光的材料。＜Liquid crystal alignment film＞ The liquid crystal alignment film of the present invention is a film obtained by coating the above-mentioned liquid crystal alignment agent on a substrate, drying, and firing. The substrate on which the liquid crystal alignment agent of the present invention is coated is not particularly limited as long as it has high transparency. Plastic substrates such as glass substrates, silicon nitride substrates, acrylic substrates, and polycarbonate substrates can be used. , it is preferable to use a substrate on which ITO electrodes for driving liquid crystal are formed, from the viewpoint of simplification of the manufacturing process. In addition, reflective liquid crystal display elements have only one side of the substrate, so they can also use opaque materials such as silicon wafers. In this case, the electrodes can also use materials that can reflect light, such as aluminum.

作為本發明的液晶配向劑的塗佈方法，可舉出旋轉塗佈法、印刷法、噴墨法等。塗佈本發明的液晶配向劑後的乾燥、燒成步驟係可選擇任意的溫度與時間。通常為了充分去除所含有的有機溶劑，以50℃~120℃使其乾燥1分鐘~10分鐘，之後再以150℃~300℃燒成5分鐘~120分鐘。燒成後的塗膜的厚度並無特別限定，若過薄時則會有液晶顯示元件的可靠性降低之情形，因此以5~300nm，較佳為10~200nm。Examples of methods for applying the liquid crystal alignment agent of the present invention include spin coating, printing, inkjet, and the like. Any temperature and time can be selected for the drying and firing steps after coating the liquid crystal alignment agent of the present invention. Usually, in order to fully remove the organic solvent contained, it is dried at 50°C to 120°C for 1 minute to 10 minutes, and then fired at 150°C to 300°C for 5 minutes to 120 minutes. The thickness of the fired coating film is not particularly limited. If it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, the thickness is 5 to 300 nm, preferably 10 to 200 nm.

作為將所得到的液晶配向膜進行配向處理之方法，可舉出摩擦法、光配向處理法等。摩擦處理係可利用既有的摩擦裝置來進行。作為此時的摩擦布材質，可舉出棉、尼龍、嫘縈等。作為摩擦處理的條件係通常可使用旋轉速度300~2000rpm、送入速度5~100mm/s、壓入量0.1~1.0mm之類條件。之後，使用純水或醇等藉由超音波洗淨，來去除因摩擦所產生的殘渣。Examples of methods for subjecting the obtained liquid crystal alignment film to alignment treatment include rubbing methods, photo-alignment treatment methods, and the like. The friction treatment can be performed using existing friction equipment. Examples of the friction cloth material at this time include cotton, nylon, rayon, and the like. As conditions for the friction treatment, conditions such as a rotation speed of 300 to 2000 rpm, a feed speed of 5 to 100 mm/s, and an indentation amount of 0.1 to 1.0 mm are generally used. Afterwards, use pure water or alcohol to clean with ultrasonic waves to remove the residue caused by friction.

作為光配向處理法的具體例，可舉出對前述塗膜表面照射一定方向偏向的放射線，依照各種情形進而以150~250℃的溫度進行加熱處理，從而賦予液晶配向能之方法。作為放射線係可使用具有100~800nm的波長的紫外線及可見光線。其中，以具有100~400nm的波長的紫外線為較佳，以具有200~400nm的波長者為特佳。又，為了改善液晶配向性，亦可將塗膜基板以50~250℃一邊加熱，一邊照射放射線。前述放射線的照射量係以1~10,000mJ/ cm² 為較佳，以100~5,000mJ/cm² 為特佳。以上述般之方式所製作的液晶配向膜，可使液晶分子朝一定方向穩定地配向。偏光的紫外線的消光比越高，則可賦予越高的異向性，故為較佳。具體而言，直線偏光的紫外線的消光比係以10：1以上為較佳，以20：1以上為又較佳。As a specific example of the photo-alignment treatment method, there is a method of irradiating the surface of the above-mentioned coating film with radiation oriented in a certain direction, and then performing a heat treatment at a temperature of 150 to 250° C. in various cases to impart alignment ability to the liquid crystal. As the radiation system, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm are preferred, and those having a wavelength of 200 to 400 nm are particularly preferred. In addition, in order to improve the liquid crystal alignment, the coated substrate may be heated at 50 to 250°C while being irradiated with radiation. The irradiation dose of the aforementioned radiation is preferably 1~10,000mJ/ ^cm2 , and particularly preferably 100~5,000mJ/ ^cm2 . The liquid crystal alignment film produced in the above manner can stably align liquid crystal molecules in a certain direction. The higher the extinction ratio of polarized ultraviolet rays, the higher the anisotropy can be imparted, which is preferable. Specifically, the extinction ratio of linearly polarized ultraviolet rays is preferably 10:1 or more, and still more preferably 20:1 or more.

上述，經照射偏光的放射線的膜，接下來亦可利用包含選自水及有機溶劑中的至少1種的溶劑來進行接觸處理。作為接觸處理中使用的溶劑，只要是可溶解因光照射而生成的分解物的溶劑即可，並無特別限定。作為具體例，可舉出水、甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮、1-甲氧基-2-丙醇、1-甲氧基-2-丙醇乙酸酯、丁基賽路蘇、乳酸乙酯、乳酸甲酯、二丙酮醇、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸丙酯、乙酸丁酯、及乙酸環己酯等。該等的溶劑亦可併用2種以上。就廣用性或安全性之觀點而言，以選自由水、2-丙醇、1-甲氧基-2-丙醇及乳酸乙酯所成的群組中的至少1種為又較佳。以水、2-丙醇、及水與2-丙醇的混合溶劑為特佳。As described above, the film that has been irradiated with polarized radiation may then be subjected to contact treatment with a solvent containing at least one selected from water and organic solvents. The solvent used in the contact treatment is not particularly limited as long as it can dissolve decomposition products generated by light irradiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, and 1-methoxy-2-propanol acetate. , butylcerosin, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cycloacetate Hexyl ester etc. Two or more types of these solvents may be used in combination. From the viewpoint of broad applicability or safety, at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol, and ethyl lactate is more preferred. . Water, 2-propanol, and a mixed solvent of water and 2-propanol are particularly preferred.

本發明中，經照射偏光的放射線的膜與包含有機溶劑的溶液的接觸處理，能以浸漬處理、噴霧(spray)處理等的，膜與溶液可較佳充分接觸之類的處理來進行。其中，在包含有機溶劑的溶液中，將膜較佳以10秒鐘~1小時，又較佳以1~30分鐘的浸漬處理之方法為較佳。接觸處理可為常溫亦可以是加溫下進行，較佳以10~80℃，又較佳以20~50℃來實施。又，因應所需可施予超音波等的提高接觸之手段。於上述接觸處理後，就去除所使用的溶液中的有機溶劑之目的，可進行藉由水、甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮等的低沸點溶劑之水洗(淋洗)或乾燥中之任一者、或兩者。In the present invention, the contact treatment between a film irradiated with polarized radiation and a solution containing an organic solvent can be performed by a treatment such as a immersion treatment or a spray treatment, so that the film and the solution are preferably fully contacted. Among them, the method of immersing the membrane in a solution containing an organic solvent is preferably 10 seconds to 1 hour, and more preferably 1 to 30 minutes. The contact treatment can be carried out at normal temperature or under heating, preferably at 10 to 80°C, and more preferably at 20 to 50°C. In addition, contact-enhancing means such as ultrasound can be used as needed. After the above contact treatment, for the purpose of removing the organic solvent in the solution used, water washing (leaching) with low boiling point solvents such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, etc. either washing) or drying, or both.

進而，經上述藉由溶劑的接觸處理的膜，就使溶劑的乾燥及膜中的分子鏈進行再配向為目的，亦可再以150℃以上來進行加熱。作為加熱的溫度係以150~300℃為較佳。溫度越高雖會促進分子鏈的再配向，但溫度過高時將會有伴隨分子鏈的分解之虞。因此，作為加熱溫度係以180~250℃為又較佳，以200~230℃為特佳。加熱時間越短時，將會有無法得到分子鏈再配向之效果的可能性，但過長時，因分子鏈將會有分解的可能性，故以10秒鐘~30分鐘為較佳，以1~10分鐘為又較佳。Furthermore, the film that has been subjected to the above-mentioned contact treatment with a solvent may be further heated at 150° C. or higher for the purpose of drying the solvent and realigning the molecular chains in the film. The heating temperature is preferably 150 to 300°C. Although higher temperatures will promote the realignment of molecular chains, when the temperature is too high, there is a risk of decomposition of the molecular chains. Therefore, the heating temperature is preferably 180 to 250°C, and particularly preferably 200 to 230°C. If the heating time is shorter, there is a possibility that the effect of realignment of the molecular chains cannot be obtained. However, if the heating time is too long, the molecular chains may be decomposed, so 10 seconds to 30 minutes is better. 1~10 minutes is better.

＜液晶顯示元件＞本發明的液晶顯示元件，其特徵在於具備藉由前述液晶配向膜的製造方法所得到的液晶配向膜。本發明的液晶顯示元件係將本發明的液晶配向劑藉由前述液晶配向膜的製造方法，來得到附帶液晶配向膜的基板後，利用周知之方法來製作液晶晶胞，並使用其來作為液晶顯示元件。＜Liquid crystal display element＞ The liquid crystal display element of the present invention is characterized by including a liquid crystal alignment film obtained by the above-mentioned manufacturing method of a liquid crystal alignment film. The liquid crystal display element of the present invention uses the liquid crystal alignment agent of the present invention through the aforementioned manufacturing method of a liquid crystal alignment film to obtain a substrate with a liquid crystal alignment film, and then uses a well-known method to produce a liquid crystal cell and uses it as a liquid crystal Display components.

作為液晶晶胞製作方法之一例，將以被動矩陣構造的液晶顯示元件為例來做說明。尚，構成畫面顯示的各像素部分，亦可為設置有TFT(Thin Film Transistor)等的切換元件的主動矩陣構造的液晶顯示元件。首先，準備透明的玻璃製的基板，在一側的基板上設置共用電極，在另一側的基板上設置節段電極。該等的電極係可設為例如ITO電極，並以經圖型化來形成所期望的畫面顯示。接下來，在各基板上以被覆共用電極與節段電極之方式來設置絕緣膜。絕緣膜係可設為藉由例如溶膠-凝膠法所形成的由SiO₂ -TiO₂ 所成的膜。接下來，在各基板上形成本發明的液晶配向膜。接下來，將一側的基板與另一側的基板以互相的配向膜面對向之方式來進行重疊，並利用密封材來接著周邊。為了控制基板間隙，密封材中通常為混入有間隔件。又，未設置密封材的面內部分，亦以散布基板間隙控制用的間隔件為較佳。密封材的一部分為被設置有可由外部填充液晶的開口部。接下來，通過設置於密封材的開口部，將液晶材料注入於由2片的基板與密封材所包圍的空間內。之後，將該開口部利用接著劑密封。注入亦可使用真空注入法，亦可使用在大氣中利用毛細管現象之方法。接下來，進行偏光板的設置。具體而言在相對於2片的基板的液晶層為相反側之面上貼附一對偏光板。經由以上的步驟可得到本發明的液晶顯示元件。As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element with a passive matrix structure will be taken as an example for explanation. Furthermore, each pixel portion constituting the screen display may be an active matrix structure liquid crystal display element provided with a switching element such as a TFT (Thin Film Transistor). First, a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate. The electrodes can be, for example, ITO electrodes, and can be patterned to form a desired screen display. Next, an insulating film is provided on each substrate to cover the common electrode and the segment electrode. The insulating film system may be a film composed of SiO ₂ -TiO ₂ formed by, for example, a sol-gel method. Next, the liquid crystal alignment film of the present invention is formed on each substrate. Next, the substrate on one side and the substrate on the other side are overlapped so that the alignment film surfaces face each other, and a sealing material is used to connect the periphery. In order to control the substrate gap, spacers are usually mixed into the sealing material. In addition, it is also preferable to spread spacers for substrate gap control in the in-plane portion where the sealing material is not provided. A part of the sealing material is provided with an opening through which liquid crystal can be filled from the outside. Next, the liquid crystal material is injected into the space surrounded by the two substrates and the sealing material through the opening provided in the sealing material. Thereafter, the opening is sealed with an adhesive. Vacuum injection method can also be used for injection, or a method utilizing capillary phenomenon in the atmosphere can be used. Next, set up the polarizer. Specifically, a pair of polarizing plates are attached to the surface of the two substrates on the opposite side to the liquid crystal layer. Through the above steps, the liquid crystal display element of the present invention can be obtained.

本發明中，作為密封劑可使用具有例如環氧基、丙烯醯基、甲基丙烯醯基、羥基、烯丙基、乙醯基等的反應性基的藉由紫外線照射或加熱而硬化的樹脂。特別是以使用具有環氧基與(甲基)丙烯醯基的兩者的反應性基的硬化樹脂系為較佳。本發明的密封劑，就以接著性、耐濕性的提升為目的亦可調配無機填充劑。作為能夠使用的無機填充劑並無特別限定，具體而言可舉出球狀二氧化矽、熔融二氧化矽、結晶二氧化矽、氧化鈦、鈦黑、碳化矽、氮化矽、氮化硼、碳酸鈣、碳酸鎂、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氧化鎂、氧化鋯、氫氧化鋁、矽酸鈣、矽酸鋁、矽酸鋰鋁、矽酸鋯、鈦酸鋇、硝子纖維、碳纖維、二硫化鉬、石棉等，較佳為球狀二氧化矽、熔融二氧化矽、結晶二氧化矽、氧化鈦、鈦黑、氮化矽、氮化硼、碳酸鈣、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氫氧化鋁、矽酸鈣、矽酸鋁。前述的無機填充劑係可混合2種以上來使用。 [實施例]In the present invention, a resin that is cured by ultraviolet irradiation or heating and has a reactive group such as an epoxy group, an acrylic group, a methacrylic group, a hydroxyl group, an allyl group, an acetyl group, etc. can be used as the sealing agent. . In particular, it is preferable to use a cured resin system having reactive groups of both an epoxy group and a (meth)acrylyl group. The sealant of the present invention can also contain an inorganic filler for the purpose of improving adhesion and moisture resistance. The inorganic filler that can be used is not particularly limited, and specific examples include spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon carbide, silicon nitride, and boron nitride. , calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, titanium Barium acid, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon nitride, boron nitride, calcium carbonate , barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, aluminum hydroxide, calcium silicate, aluminum silicate. The above-mentioned inorganic filler system can mix and use 2 or more types. [Example]

以下為舉出實施例等來對於本發明進行具體地說明，但本發明並非被限定於該等的實施例中。尚，化合物的簡略符號的意思係如下述般。 The present invention will be described in detail below with reference to examples and the like, but the present invention is not limited to these examples. However, the abbreviated symbols for compounds have the following meanings.

NMP：N-甲基-2-吡咯啶酮(N-methyl-2-pyrrolidone) BCS：丁基賽路蘇(butyl cellosolve) THF：四氫呋喃 AIBN：2,2’-偶氮雙異丁腈NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve THF: Tetrahydrofuran AIBN: 2,2’-azobisisobutyronitrile

(¹ H-NMR之測定) 裝置：Varian NMR system 400NB(400MHz)(Varian公司製)、及JMTC-500/54/SS(500MHz)(JEOL公司製) 測定溶劑：CDCl₃ (重氫化三氯甲烷)，DMSO-d₆ (重氫化二甲基亞碸) 基準物質：TMS(四甲基矽烷)(δ：0.0ppm，¹ H)及CDCl₃ (δ：77.0ppm，¹³ C)(Measurement of ¹ H-NMR) Device: Varian NMR system 400NB (400MHz) (manufactured by Varian Corporation), and JMTC-500/54/SS (500MHz) (manufactured by JEOL Corporation) Measurement solvent: CDCl ₃ (deuterated chloroform) ), DMSO-d ₆ (deuterated dimethylstyrene) reference materials: TMS (tetramethylsilane) (δ: 0.0ppm, ¹ H) and CDCl ₃ (δ: 77.0ppm, ¹³ C)

＜添加劑E1之合成＞在甲苯(25g)及純水(2.5g)中，加入環氧氯丙烷(52.1g)及4,4’-二胺基-N-甲基二苯基胺(10.0g、46.9mmol)，並以80℃攪拌4小時。冷卻至室溫後，加入硫酸氫四丁基銨(0.48g)及48%氫氧化鈉水溶液(23.5g)，以35℃攪拌3小時後，再以室溫攪拌16小時。加入純水(50g)並進行分液操作，利用純水(50g)洗淨油層，藉由利用硫酸鎂進行脫水並濃縮濾液從而得到粗產物。利用甲苯(150g)使粗產物溶解後，使用過濾面為填充有二氧化矽凝膠(20g)的桐山漏斗(Hirsch funnel)來進行過濾。進而，將甲苯(50g)沖走後，藉由將合併的濾液濃縮從而得到化合物[E1](收量：13.2g、收率：64%、茶色黏性物)。 1H-NMR(400MHz, DMSO-d6, δppm)：6.78-6.73(m, 8H), 3.59(t, 4H, J = 16 Hz), 3.38-3.26(m, 4H), 3.13-3.04(m, 7H), 2.75-2.71(m, 4H), 2.58-2.55(m, 4H).＜Synthesis of Additive E1＞ To toluene (25g) and pure water (2.5g), add epichlorohydrin (52.1g) and 4,4'-diamino-N-methyldiphenylamine (10.0g, 46.9mmol), and Stir at 80°C for 4 hours. After cooling to room temperature, tetrabutylammonium hydrogen sulfate (0.48g) and 48% sodium hydroxide aqueous solution (23.5g) were added, and the mixture was stirred at 35°C for 3 hours, and then stirred at room temperature for 16 hours. Pure water (50g) was added and liquid separation was performed. The oil layer was washed with pure water (50g), and the crude product was obtained by dehydrating with magnesium sulfate and concentrating the filtrate. The crude product was dissolved in toluene (150 g), and then filtered using a Hirsch funnel with a filter surface filled with silica gel (20 g). Furthermore, after toluene (50 g) was washed away, the combined filtrate was concentrated to obtain compound [E1] (amount: 13.2 g, yield: 64%, brown viscous substance). 1H-NMR (400MHz, DMSO-d6, δppm): 6.78-6.73(m, 8H), 3.59(t, 4H, J = 16 Hz), 3.38-3.26(m, 4H), 3.13-3.04(m, 7H ), 2.75-2.71(m, 4H), 2.58-2.55(m, 4H).

＜添加劑E2之合成＞在甲苯(25g)及純水(2.5g)中，加入環氧氯丙烷(55.4g)及4,4’-二胺基二苯基醚(10.0g、49.9mmol)，並以80℃攪拌23小時。冷卻至室溫後，加入硫酸氫四丁基銨(0.51g)及48%氫氧化鈉水溶液(25.0g)，以35℃攪拌5小時。加入純水(50g)並進行分液操作，利用純水(50g)洗淨油層，藉由利用硫酸鎂進行脫水並濃縮濾液從而得到粗產物。利用甲苯(150g)使粗產物溶解後，使用過濾面為填充有二氧化矽凝膠(20g)的桐山漏斗來進行過濾。進而，將甲苯(50g)沖走後，藉由將合併的濾液濃縮從而得到化合物[E2](收量：15.3g、收率：72%、橙色黏性物)。 1H-NMR(400MHz, DMSO-d6, δppm)：6.84-6.80(m, 8H), 3.64(t, 4H, J = 16 Hz), 3.40-3.28(m, 4H), 3.14-3.08(m, 4H), 2.76-2.72(m, 4H), 2.59-2.56(m, 4H).＜Synthesis of Additive E2＞ To toluene (25g) and pure water (2.5g), epichlorohydrin (55.4g) and 4,4'-diaminodiphenyl ether (10.0g, 49.9mmol) were added, and stirred at 80°C for 23 hours. After cooling to room temperature, tetrabutylammonium hydrogen sulfate (0.51g) and 48% sodium hydroxide aqueous solution (25.0g) were added, and the mixture was stirred at 35°C for 5 hours. Pure water (50g) was added and liquid separation was performed. The oil layer was washed with pure water (50g), and the crude product was obtained by dehydrating with magnesium sulfate and concentrating the filtrate. The crude product was dissolved in toluene (150 g), and then filtered using a Kiriyama funnel with a filter surface filled with silica gel (20 g). Furthermore, after toluene (50 g) was washed away, the combined filtrate was concentrated to obtain compound [E2] (amount: 15.3 g, yield: 72%, orange viscous substance). 1H-NMR (400MHz, DMSO-d6, δppm): 6.84-6.80(m, 8H), 3.64(t, 4H, J = 16 Hz), 3.40-3.28(m, 4H), 3.14-3.08(m, 4H ), 2.76-2.72(m, 4H), 2.59-2.56(m, 4H).

＜黏度＞合成例中，聚合物溶液的黏度係使用E型黏度計TVE-22H(東機產業公司製)，以樣品量1.1mL、錐形轉子TE-1(1°34’、R24)、溫度25℃來進行測定。＜Viscosity＞ In the synthesis example, the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Industrial Co., Ltd.) with a sample volume of 1.1 mL, a conical rotor TE-1 (1°34', R24), and a temperature of 25°C. to measure.

(合成例1) 在附帶攪拌裝置及氮導入管的5L四頸燒瓶中，量取57.3g 的DA-1 (200mmol)，加入1147g 的NMP，一邊送氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加29.4g的CA-1 (150mmol)，再加入191g的NMP，並在氮環境下以23℃攪拌1小時。之後，量取119.3g 的DA-2 (400mmol)、60.1g 的DA-3 (400mmol)，並加入1721g的NMP，一邊送氮一邊攪拌來使其溶解。將該二胺溶液在水冷下一邊攪拌一邊添加158.8g的CA-1(810mmol)，再加入765g的NMP，並在氮環境下23℃攪拌6小時，從而得到聚醯胺酸溶液(黏度為180mPa・s)。(Synthesis example 1) In a 5L four-necked flask equipped with a stirring device and a nitrogen introduction tube, 57.3g of DA-1 (200mmol) was measured, 1147g of NMP was added, and the mixture was stirred while supplying nitrogen to dissolve it. While stirring the diamine solution under water cooling, 29.4 g of CA-1 (150 mmol) was added, and then 191 g of NMP was added, and the mixture was stirred at 23° C. for 1 hour in a nitrogen atmosphere. Thereafter, 119.3 g of DA-2 (400 mmol) and 60.1 g of DA-3 (400 mmol) were measured, and 1721 g of NMP were added and stirred to dissolve while supplying nitrogen. Add 158.8g of CA-1 (810mmol) to the diamine solution while stirring under water cooling, then add 765g of NMP, and stir at 23°C for 6 hours in a nitrogen environment to obtain a polyamide acid solution (viscosity: 180mPa・s).

(合成例2) 將MA1(5.3g)、MA2(19.6g) 溶解在THF(102.6g)中，利用隔膜泵進行脫氣後，加入AIBN(0.39g)再次進行脫氣。之後，以60℃使其反應8小時從而得到甲基丙烯酸酯的聚合物溶液。將該聚合物溶液滴入在甲醇(600ml)中，過濾所得到的沉澱物。將該沉澱物利用甲醇來洗淨，在40℃的烘箱中進行減壓乾燥，從而得到甲基丙烯酸酯聚合物粉末MP1。(Synthesis example 2) MA1 (5.3g) and MA2 (19.6g) were dissolved in THF (102.6g), and after degassing using a diaphragm pump, AIBN (0.39g) was added and degassed again. Thereafter, the mixture was reacted at 60° C. for 8 hours to obtain a methacrylate polymer solution. The polymer solution was dropped into methanol (600 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure in an oven at 40° C. to obtain methacrylate polymer powder MP1.

[實施例1]及[比較例1、2] 以所得到的液晶配向劑的組成成為表1所表示的組成之方式，一邊攪拌合成例1所得到的聚醯胺酸溶液，一邊加入溶劑及添加劑，進而藉由在室溫下攪拌2小時，從而得到液晶配向劑。 ※1：表示相對於液晶配向劑中的全聚合物100重量份的各聚合物的含有量(重量份)。 ※2：表示相對於液晶配向劑中的全聚合物100重量份的各添加劑的含有量(重量份)。 ※3：表示相對於液晶配向劑100質量份的各溶劑的含有量(重量份)。[Example 1] and [Comparative Examples 1, 2] The liquid crystal alignment agent was prepared in the form of a composition as shown in Table 1. The polyamine solution obtained in Synthesis Example 1 was stirred while adding a solvent and an additive. The mixture was stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent. ※1: Indicates the content (parts by weight) of each polymer relative to 100 parts by weight of all polymers in the liquid crystal alignment agent. ※2: Indicates the content (parts by weight) of each additive relative to 100 parts by weight of all polymers in the liquid crystal alignment agent. ※3: Indicates the content (parts by weight) of each solvent relative to 100 parts by weight of the liquid crystal alignment agent.

[實施例2]及[比較例3、4] 在合成例2所得到的甲基丙烯酸酯粉末中加入NMP，使其攪拌30分鐘，從而得到甲基丙烯酸酯聚合物溶液。以所得到的液晶配向劑的組成成為表2所表示的組成之方式，一邊攪拌一邊加入溶劑及添加劑，進而藉由在室溫下攪拌2小時，從而得到液晶配向劑。 ※1：表示相對於液晶配向劑中的全聚合物100重量份的各聚合物的含有量(重量份)。 ※2：表示相對於液晶配向劑中的全聚合物100重量份的各添加劑的含有量(重量份)。 ※3：表示相對於液晶配向劑100質量份的各溶劑的含有量(重量份)。[Example 2] and [Comparative Examples 3 and 4] NMP was added to the methacrylate powder obtained in Synthesis Example 2 and stirred for 30 minutes to obtain a methacrylate polymer solution. The solvent and additives were added while stirring so that the composition of the obtained liquid crystal alignment agent would become the composition shown in Table 2, and the liquid crystal alignment agent was obtained by stirring at room temperature for 2 hours. *1: Indicates the content (parts by weight) of each polymer relative to 100 parts by weight of the total polymer in the liquid crystal alignment agent. *2: Indicates the content (parts by weight) of each additive relative to 100 parts by weight of the total polymer in the liquid crystal alignment agent. *3: Indicates the content (parts by weight) of each solvent relative to 100 parts by mass of the liquid crystal alignment agent.

於下為表示用來評估累積電荷的緩和特性、閃爍(flicker)特性、液晶配向性的液晶晶胞的製作方法。製作具備FFS方式的液晶顯示元件的構成的液晶晶胞。首先，準備帶有電極的基板。基板係長30mm、寬35mm、厚度0.7mm的玻璃基板。在基板上，作為第1層為整面形成構成對置電極的IZO電極。在第1層的對置電極上，作為第2層為形成藉由CVD法所成膜的SiN(氮化矽)膜。第2層的SiN膜的膜厚為500nm，發揮作為層間絕緣膜的機能。在第2層的SiN膜上，作為第3層，配置將IZO膜圖型化而形成的梳齒狀的像素電極，來形成第1像素及第2像素的2個像素。各像素的尺寸係長10mm、寬約5mm。此時，第1層的對置電極與第3層的像素電極係因第2層的SiN膜的作用而電絕緣。The following shows the manufacturing method of a liquid crystal cell used to evaluate the relaxation characteristics of accumulated charges, flicker characteristics, and liquid crystal alignment. A liquid crystal cell having a structure of an FFS-type liquid crystal display element is produced. First, prepare a substrate with electrodes. The substrate is a glass substrate with a length of 30mm, a width of 35mm, and a thickness of 0.7mm. On the substrate, an IZO electrode constituting a counter electrode was formed over the entire surface as a first layer. On the counter electrode of the first layer, a SiN (silicon nitride) film formed by a CVD method is formed as a second layer. The SiN film of the second layer has a film thickness of 500 nm and functions as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning the IZO film is arranged as a third layer to form two pixels of a first pixel and a second pixel. The size of each pixel is 10mm long and about 5mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the SiN film of the second layer.

第3層的像素電極具有排列多個中央部分彎曲的「く字」形狀的電極元件所構成的梳齒狀的形狀。各電極元件的短邊方向寬度為3μm，電極元件間的間隔為6μm。形成各像素的像素電極由排列多個中央部分為彎曲的「く字」形狀的電極元件所構成，故各像素的形狀不是長方形狀，而是具備與電極元件相同地中央部分彎曲的類似粗體字的「く字」的形狀。又，各像素係以其中央的彎曲部分為界被上下分割，而具有彎曲部分的上側的第1區域與下側的第2區域。若比較各像素的第1區域與第2區域時，構成此等的像素電極的電極元件的形成方向將為不同。即，將後述的液晶配向膜的摩擦方向作為基準之情形時，像素的第1區域中，像素電極的電極元件以呈＋10°的角度(順時針)之方式形成，像素的第2區域中，像素電極的電極元件以呈-10°的角度(順時針)之方式形成。即，各像素的第1區域與第2區域中，藉由像素電極與對置電極之間的電壓施加而誘發的液晶在基板面內的旋轉動作(面內轉向)的方向互為相反的逆方向之方式來構成。The pixel electrode of the third layer has a comb-shaped shape in which a plurality of "く"-shaped electrode elements are arranged with a central portion bent. The width of each electrode element in the transversal direction is 3 μm, and the interval between electrode elements is 6 μm. The pixel electrode that forms each pixel is composed of a plurality of electrode elements arranged in a "く" shape with a curved central part. Therefore, the shape of each pixel is not a rectangular shape, but has a similar bold shape with a curved central part like the electrode elements. The shape of the character "く". In addition, each pixel is divided up and down with a central curved portion as a boundary, and has a first region above the curved portion and a second region below the curved portion. When comparing the first region and the second region of each pixel, the formation directions of the electrode elements constituting these pixel electrodes will be different. That is, when the rubbing direction of the liquid crystal alignment film described below is used as a reference, in the first area of the pixel, the electrode elements of the pixel electrode are formed at an angle of +10° (clockwise), and in the second area of the pixel, The electrode elements of the pixel electrode are formed at an angle of -10° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotational motion (in-plane turning) of the liquid crystal in the substrate plane induced by the application of the voltage between the pixel electrode and the counter electrode are opposite to each other. composed in the direction of direction.

接著，利用孔徑1.0μm的過濾器，過濾實施例及比較例所得到的液晶配向劑後，藉由旋轉塗佈機塗佈，塗佈在已準備附帶上述電極的基板上。以80℃的加熱板上使其乾燥2分鐘後，在230℃的熱風循環式烘箱中進行20分鐘燒成，從而得到膜厚60nm的聚醯亞胺膜。利用嫘縈布來摩擦該聚醯亞胺膜 (輥直徑：120mm、輥旋轉數：500rpm、移動速度：30mm/sec、壓入長度：0.3mm、摩擦方向：相對於第3層IZO梳齒電極傾斜10°的方向)後，在純水中施予1分鐘超音波照射來進行洗淨，藉由鼓風去除水滴。之後，以80℃乾燥15分鐘，從而得到帶有液晶配向膜的基板。又，作為對向基板，與上述以相同之方式，在裏面為形成有ITO電極且具有高度4μm的柱狀間隔件的玻璃基板上亦形成聚醯亞胺膜，依與上述為相同的製程，得到附帶施予配向處理的液晶配向膜的基板。將該等2片的附帶液晶配向膜的基板作為1組，在基板上以留有液晶注入口的形式來印刷密封劑，以液晶配向膜面為面對面、摩擦方向呈逆平行之方式來黏貼另1個基板。之後，使密封劑硬化，從而製作晶胞間距為4μm的空晶胞。藉由減壓注入法，向該空晶胞注入液晶MLC-3019(Merck公司製)並密封注入口，從而得到FFS方式的液晶晶胞。之後，將所得到的液晶晶胞以120℃加熱1小時，以23℃放置一晩後，用於液晶配向性之評估。Next, the liquid crystal alignment agents obtained in the Examples and Comparative Examples were filtered using a filter with a pore size of 1.0 μm, and then applied with a spin coater to the substrate prepared with the above electrodes. After drying on a hot plate at 80° C. for 2 minutes, it was baked in a hot air circulation oven at 230° C. for 20 minutes to obtain a polyimide film with a film thickness of 60 nm. Use rayon cloth to rub the polyimide film (roller diameter: 120mm, roller rotation number: 500rpm, moving speed: 30mm/sec, pressing length: 0.3mm, rubbing direction: relative to the third layer of IZO comb electrode After tilting it in the direction of 10°), apply ultrasonic irradiation to pure water for 1 minute to wash, and remove water droplets by blowing air. Thereafter, the substrate was dried at 80° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film. In addition, as the counter substrate, in the same manner as above, a polyimide film was also formed on a glass substrate with an ITO electrode formed on the back and a columnar spacer with a height of 4 μm. According to the same process as above, A substrate with a liquid crystal alignment film subjected to alignment treatment was obtained. Take these 2 substrates with liquid crystal alignment films as a set, print the sealant on the substrate with a liquid crystal injection port, and stick the other substrates with the liquid crystal alignment film surface facing each other and the rubbing direction anti-parallel. 1 base plate. Thereafter, the sealant was hardened to produce an empty unit cell with a unit cell pitch of 4 μm. Liquid crystal MLC-3019 (manufactured by Merck Corporation) was injected into the empty cell by a reduced pressure injection method and the injection port was sealed, thereby obtaining an FFS-type liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 120°C for 1 hour and left at 23°C overnight, and then used for evaluation of liquid crystal alignment.

＜累積電荷的緩和特性＞將上述液晶晶胞設置在偏光軸為垂直方式配置的2片的偏光板之間，在使像素電極與對置電極短路且呈相同電位之狀態下，從2片的偏光板的下方照射LED背光，以在2片的偏光板的上方所測定的LED背光透過光的亮度成為最小之方式，來調節液晶晶胞的角度。接著，一邊對該液晶晶胞施加頻率30Hz的矩形波，一邊測定23℃的溫度下的V-T特性(電壓-透過率特性)，算出相對透過率為23%時的交流電壓。該交流電壓係因相當於對電壓的亮度變化為大的區域，故藉由亮度來評估累積電荷為方便。接著，在23℃的溫度，相對透過率為23%的交流電壓下，尚且施加頻率30Hz的矩形波5分鐘後，疊加＋1.0V的直流電壓，並驅動30分鐘。之後，切斷直流電壓，再次在相對透過率為23%的交流電壓下，尚且僅施加頻率30Hz的矩形波15分鐘。累積的電荷的緩和越快速的話，則疊加直流電壓時對液晶晶胞的電荷累積亦為快速，因此，累積電荷的緩和特性係以從疊加直流電壓後不久的相對透過率降低至2%以上為止所需要的時間，來進行評估。即，相對透過率在30分鐘以內降低至2%以上之情形時，則定義為「良好」；即使是經過30分鐘，相對降低率亦不會降低至2%以上之情形時，則定義為「不良」，來進行評估。＜Relaxation characteristics of accumulated charge＞ The above-mentioned liquid crystal cell is placed between two polarizing plates whose polarization axes are arranged perpendicularly. With the pixel electrode and the counter electrode short-circuited and at the same potential, LED backlight is irradiated from below the two polarizing plates. , adjust the angle of the liquid crystal cell so that the brightness of the LED backlight transmitted light measured above the two polarizing plates becomes the minimum. Next, while applying a rectangular wave with a frequency of 30 Hz to the liquid crystal cell, the V-T characteristics (voltage-transmittance characteristics) at a temperature of 23° C. were measured, and the AC voltage when the relative transmittance was 23% was calculated. This AC voltage corresponds to an area where the brightness change with respect to the voltage is large, so it is convenient to evaluate the accumulated charge based on the brightness. Then, at a temperature of 23°C and an AC voltage with a relative transmittance of 23%, a rectangular wave with a frequency of 30Hz was applied for 5 minutes, and then a DC voltage of +1.0V was superimposed and driven for 30 minutes. After that, the DC voltage was cut off, and only a rectangular wave with a frequency of 30 Hz was applied for 15 minutes under an AC voltage with a relative transmittance of 23%. If the accumulated charge is relaxed faster, the charge accumulation in the liquid crystal cell will also be faster when the DC voltage is superimposed. Therefore, the relaxation characteristics of the accumulated charge are until the relative transmittance is reduced to more than 2% from the relative transmittance shortly after the DC voltage is superimposed. The time required to make the assessment. That is, if the relative transmittance decreases to 2% or more within 30 minutes, it is defined as "good"; if the relative transmittance does not decrease to 2% or more even after 30 minutes, it is defined as "good". "Defect" for evaluation.

＜液晶配向性之評估＞使用該液晶晶胞，在60℃的恆溫環境下，施加頻率為30Hz、9VPP的交流電壓190小時。之後，使液晶晶胞的像素電極與對置電極之間發生短路之狀態下，直接以室溫下放置一天。放置後，將液晶晶胞設置在偏光軸為垂直方式配置的2片的偏光板之間，在無電壓施加之狀態下使背光點燈，以透過光的亮度成為最小之方式來調整液晶晶胞的配置角度。又，將液晶晶胞從第1像素的第2區域為最暗的角度，旋轉至第1區域為最暗的角度時，將該旋轉角度以角度Δ來算出。第2像素亦相同地，比較第2區域與第1區域，來算出同樣的角度Δ。又，將第1像素與第2像素的角度Δ值的平均值作為液晶晶胞的角度Δ來算出。該液晶晶胞的角度Δ的值若未滿0.2度之情形時，則定義為「良好」；角度Δ的值若為0.2度以上之情形時，則定義為「不良」，來進行評估。＜Evaluation of Liquid Crystal Alignment＞ Using this liquid crystal cell, an AC voltage with a frequency of 30Hz and 9VPP was applied for 190 hours in a constant temperature environment of 60°C. Thereafter, the liquid crystal cell was left at room temperature for one day in a state where a short circuit occurred between the pixel electrode and the counter electrode. After placement, the liquid crystal cell is placed between two polarizing plates with vertical polarization axes, and the backlight is turned on without applying voltage, and the liquid crystal cell is adjusted so that the brightness of the transmitted light is minimized. configuration angle. Furthermore, when the liquid crystal cell is rotated from the angle where the second area of the first pixel is the darkest to the angle where the first area is the darkest, the rotation angle is calculated as the angle Δ. Likewise for the second pixel, the second area and the first area are compared to calculate the same angle Δ. Furthermore, the average value of the angle Δ values of the first pixel and the second pixel is calculated as the angle Δ of the liquid crystal cell. If the value of the angle Δ of the liquid crystal cell is less than 0.2 degrees, it is defined as "good"; if the value of the angle Δ is more than 0.2 degrees, it is defined as "poor" for evaluation.

＜電壓保持率(VHR)之評估＞在60℃的溫度下對所得到的液晶晶胞施加1V的電壓60μs，測定50ms後的電壓，從而計算電壓可保持多少來作為電壓保持率。尚，電壓保持率之測定係使用TOYO Corporation製的電壓保持率測定裝置VHR-1。＜Evaluation of Voltage Holding Ratio (VHR)＞ A voltage of 1 V was applied to the obtained liquid crystal cell at a temperature of 60° C. for 60 μs, and the voltage after 50 ms was measured to calculate how much the voltage could be maintained as the voltage retention rate. Note that the voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by TOYO Corporation.

＜光學特性(透明性)之評估＞準備長40mm、寬40mm、厚度1.0mm的石英基板。接下來，利用1.0μm的過濾器來過濾液晶配向劑後，旋轉塗佈在上述石英基板上。接下來，在80℃的加熱板上乾燥2分鐘後，以230℃燒成20分鐘，從而在各基板上得到膜厚100nm的聚醯亞胺膜。透明性之評估係藉由測定依前述方法所得到的基板的透過率來進行。具體而言，測定裝置為使用UV-3600(島津製作所公司製)，以溫度25℃、掃描波長設為300~800nm之條件下來測定透過率。此時，作為基準(參考例)係使用未塗佈的石英基板來進行。評估係算出400~800nm的波長的平均透過率，透過率越高者，則透明性視為越優異。<Evaluation of optical properties (transparency)> Prepare a quartz substrate with a length of 40mm, a width of 40mm, and a thickness of 1.0mm. Next, after filtering the liquid crystal alignment agent with a 1.0 μm filter, the liquid crystal alignment agent was spin-coated on the quartz substrate. Next, after drying on a hot plate at 80° C. for 2 minutes, it was baked at 230° C. for 20 minutes, thereby obtaining a polyimide film with a film thickness of 100 nm on each substrate. The transparency is evaluated by measuring the transmittance of the substrate obtained according to the aforementioned method. Specifically, the measuring device used UV-3600 (manufactured by Shimadzu Corporation) to measure the transmittance under the conditions of a temperature of 25° C. and a scanning wavelength of 300 to 800 nm. At this time, an uncoated quartz substrate was used as a standard (reference example). The evaluation is based on calculating the average transmittance at a wavelength of 400 to 800 nm. The higher the transmittance, the better the transparency.

＜評估結果＞關於使用上述實施例1~4、及比較例1~3的各液晶配向劑之液晶顯示元件，將上述所實施的殘影消失時間之評估、液晶配向之穩定性之評估、及透明性之評估之結果表示於表3。 ※1：表示相對於液晶配向劑中的全聚合物100重量份的各聚合物的含有量(重量份)。 ※2：表示相對於液晶配向劑中的全聚合物100重量份的各添加劑的含有量(重量份)。<Evaluation results> Regarding the liquid crystal display elements using each of the liquid crystal alignment agents of Examples 1 to 4 and Comparative Examples 1 to 3, the above-mentioned evaluation of the disappearance time of the residual image, the evaluation of the stability of the liquid crystal alignment, and The results of the transparency assessment are shown in Table 3. *1: Indicates the content (parts by weight) of each polymer relative to 100 parts by weight of the total polymer in the liquid crystal alignment agent. *2: Indicates the content (parts by weight) of each additive relative to 100 parts by weight of the total polymer in the liquid crystal alignment agent.

如表3所示可得知，使用實施例1的液晶配向劑的液晶顯示元件係電壓保持率為優異、累積電荷的緩和為快速，且液晶配向性或透明性為良好。 [產業利用性]As shown in Table 3, it can be seen that the liquid crystal display element using the liquid crystal alignment agent of Example 1 has excellent voltage retention, rapid relaxation of accumulated charges, and good liquid crystal alignment or transparency. [Industrial Applicability]

本發明的液晶配向劑係被廣泛使用於TN方式、VA方式等的縱向電場方式，特別是IPS方式、FFS方式等的橫向電場方式的液晶顯示元件。尚，將2018年3月19日所提出專利申請的日本特願2018-51092號的說明書、申請專利範圍、及摘要的全部內容援用於此，以採用作為本發明的說明書的揭示內容。The liquid crystal alignment agent of the present invention is widely used in vertical electric field mode liquid crystal display elements such as TN mode and VA mode, and particularly in transverse electric field mode liquid crystal display elements such as IPS mode and FFS mode. The entire contents of the specification, patent scope, and abstract of Japanese Patent Application No. 2018-51092 filed on March 19, 2018 are hereby incorporated by reference, and the disclosure content of the specification shall be adopted as the specification of the present invention.

Claims

一種液晶配向劑，其特徵在於含有下述(A)成分、(B)成分及有機溶劑，(A)成分：選自由聚醯亞胺前驅物、該聚醯亞胺前驅物的醯亞胺化聚合物及在100~300℃的溫度範圍內展現出液晶性的感光性側鏈型丙烯酸聚合物所成的群組中的至少1種的聚合物；(B)成分：選自下述式Q1-1-1~式Q1-1-4及式Q1-1-6中的至少1種，

A liquid crystal alignment agent, characterized by containing the following (A) component, (B) component and an organic solvent, (A) component: selected from the group consisting of a polyimide precursor and the imidization of the polyimide precursor. At least one polymer from the group consisting of a polymer and a photosensitive side chain acrylic polymer exhibiting liquid crystallinity in a temperature range of 100 to 300°C; (B) component: selected from the following formula Q1 -1-1~at least one of formula Q1-1-4 and formula Q1-1-6,

如請求項1之液晶配向劑，其中，前述(A)成分的聚醯亞胺前驅物具有下述式(A1)所表示的構造單位，

(式(A1)中，X₁為四價有機基，Y₁為二價有機基，R₁為氫原子或碳數1~5的烷基，A₁及A₂分別獨立為氫原子、可具有取代基的碳數1~10的烷基、可具有取代基的碳數2~10的烯基或可具有取代基的碳數2~10的炔基)。 The liquid crystal alignment agent of claim 1, wherein the polyimide precursor of component (A) has a structural unit represented by the following formula (A1),

₍ _In formula ₍ _A1 ₎ , An alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, or an alkynyl group having 2 to 10 carbon atoms which may have a substituent).

如請求項2之液晶配向劑，其中，前述式(A1)中，Y₁為選自下述式所表示的構造(5)及式(6)所表示的構造中的至少1種，

(式(5)中，R₁₂為單鍵或碳數1~30的二價有機基，R₁₃為氫原子、鹵素原子或碳數1~30的一價有機基，a為1~4的整數，當a為2以上時，2個以上的R₁₂及2個以上的R₁₂R₁₃可為相同或相異；式(6)中，R₁₄為-O-、-S-、-NR₁₅-或碳數1~40的二價有機基，R₁₅為氫原子)。 The liquid crystal alignment agent of claim 2, wherein in the aforementioned formula (A1), Y ₁ is at least one selected from the structure (5) represented by the following formula and the structure represented by the formula (6),

(In formula (5), R ₁₂ is a single bond or a divalent organic group with 1 to 30 carbon atoms, R ₁₃ is a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 30 carbon atoms, and a is 1 to 4 Integer, when a is 2 or more, more than 2 R ₁₂ and more than 2 R ₁₂ R ₁₃ can be the same or different; in formula (6), R ₁₄ is -O-, -S-, -NR ₁₅ - or a divalent organic radical with 1 to 40 carbon atoms, R ₁₅ is a hydrogen atom).

如請求項1之液晶配向劑，其中，前述(A)成分的在100~300℃的溫度範圍內展現出液晶性的感光性側鏈型丙烯酸聚合物具有由下述式(i)~(v)的至少1種所成的側鏈構造，

(式(i)~(v)中，Ar₁為從苯環、萘環、吡咯環、呋喃環、噻吩環或吡啶環之中去除2個氫原子而成的二價取代基，Ar₂及Ar₃分別獨立為從苯環、萘環、吡咯環、呋喃環、噻吩環或吡啶環之中去除2個氫原子而成的二價取代基，q1與q2之一方為1，另一方為0，Ar₄及Ar₅分別獨立表示從苯環、萘環、吡咯環、呋喃環、噻吩環或吡啶環之中去除2個氫原子而成的二價取代基，Y₁及Y₂分別獨立為-CH=CH-、-CH=N-、-N=CH-或-C≡C-，S₁、S₂及S₃分別獨立表示單鍵、碳數1~18的直鏈或分支狀的伸烷基、碳數5~8的伸環烷基、伸苯基、伸聯苯基或由該等的2~10個基的組合所成的二價取代基，尚，前述S₁、S₂及S₃的二價取代基亦可為介隔單鍵、醚鍵、酯鍵、醯胺鍵、尿素鍵、胺基甲酸酯鍵、胺基鍵、羰基鍵來將分別的複數個二價取代基予以連結而成的構造，R₁₁為氫原子、羥基、巰基、胺基、碳數1~10的烷基、碳數1~10的烷氧基、碳數1~8的烷基胺基或碳數2~16的二烷基胺基)。 The liquid crystal alignment agent of claim 1, wherein the photosensitive side chain acrylic polymer of the component (A) exhibiting liquid crystallinity in the temperature range of 100 to 300°C has the following formulas (i) to (v ), a side chain structure composed of at least one of

(In formulas (i) to (v), Ar ₁ is a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, naphthalene ring, pyrrole ring, furan ring, thiophene ring or pyridine ring, Ar ₂ and Ar ₃ is independently a divalent substituent formed by removing two hydrogen atoms from a benzene ring, naphthalene ring, pyrrole ring, furan ring, thiophene ring or pyridine ring. One of q1 and q2 is 1, and the other is 0. , Ar ₄ and Ar ₅ independently represent a divalent substituent formed by removing two hydrogen atoms from a benzene ring, naphthalene ring, pyrrole ring, furan ring, thiophene ring or pyridine ring, Y ₁ and Y ₂ are independently -CH=CH-, -CH=N-, -N=CH- or -C≡C-, S ₁ , S ₂ and S ₃ independently represent single bonds, linear or branched chains with 1 to 18 carbon atoms. Alkylene group, cycloalkylene group with 5 to 8 carbon atoms, phenylene group, biphenyl group or a divalent substituent composed of a combination of 2 to 10 of these groups, S ₁ , S mentioned above The divalent substituents of ₂ and S ₃ can also be intervening single bonds, ether bonds, ester bonds, amide bonds, urea bonds, urethane bonds, amine bonds, and carbonyl bonds to separate the respective plurality of two. A structure in which valent substituents are linked together. R ₁₁ is a hydrogen atom, a hydroxyl group, a mercapto group, an amine group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. Amino group or dialkylamino group with 2 to 16 carbon atoms).

如請求項1~4中任一項之液晶配向劑，其中，前述有機溶劑為N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、二甲亞碸、γ-丁內酯、1,3-二甲基-咪唑啶酮、甲基乙基酮、環己酮、環戊酮或4-羥基-4-甲基-2-戊酮。 The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the aforementioned organic solvent is N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2- Pyrrolidone, N-ethyl-2-pyrrolidone, dimethyltrisoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentyl ketone or 4-hydroxy-4-methyl-2-pentanone.

如請求項5之液晶配向劑，其中，前述有機溶劑進一步包含用來提升液晶配向膜的塗膜性或表面平滑性的溶劑。 The liquid crystal alignment agent of claim 5, wherein the organic solvent further includes a solvent used to improve the coating properties or surface smoothness of the liquid crystal alignment film.

如請求項1~4中任一項之液晶配向劑，其中，液晶配向劑中含有1~10質量%的包含前述(A)成分的聚合物。 The liquid crystal alignment agent of any one of claims 1 to 4, wherein the liquid crystal alignment agent contains 1 to 10 mass % of a polymer containing the aforementioned component (A).

如請求項7之液晶配向劑，其中，相對於前述(A)成分，含有0.1~20質量%的前述(B)成分。 The liquid crystal alignment agent of claim 7, which contains 0.1 to 20 mass % of the aforementioned component (B) relative to the aforementioned component (A).

一種由請求項1~8中任一項之液晶配向劑而得到的液晶配向膜。 A liquid crystal alignment film obtained from the liquid crystal alignment agent of any one of claims 1 to 8.

一種具備請求項9之液晶配向膜的液晶顯示元件。 A liquid crystal display element provided with the liquid crystal alignment film of claim 9.