TWI656173B - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

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

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TWI656173B
TWI656173B TW103136644A TW103136644A TWI656173B TW I656173 B TWI656173 B TW I656173B TW 103136644 A TW103136644 A TW 103136644A TW 103136644 A TW103136644 A TW 103136644A TW I656173 B TWI656173 B TW I656173B
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作本直樹
山極大輝
飯沼洋介
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日商日產化學工業股份有限公司
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    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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Abstract

本發明提供一種可抑制因交流驅動的非對稱化所造成之電荷蓄積，可提早緩和因直流電壓所蓄積之殘留電荷，可抑制因交流驅動所造成之殘像的液晶配向劑、液晶配向膜。 The present invention provides a liquid crystal alignment agent and a liquid crystal alignment film which can suppress the accumulation of electric charge due to the asymmetry of the AC drive, and can repel the residual electric charge accumulated by the DC voltage, and can suppress the afterimage caused by the AC drive.

含有(A)成份及(B)成份之液晶配向劑。 A liquid crystal alignment agent containing the component (A) and the component (B).

(A)成份：具有由式[1A]及[1B]所成之群所選出之至少1種的結構之聚醯亞胺前驅物，及該聚醯亞胺前驅物經醯亞胺化所得之聚醯亞胺所成之群所選出之至少1種的聚合物。 (A) component: a polyimine precursor having a structure selected from at least one selected from the group consisting of the formulas [1A] and [1B], and a polyamidene precursor obtained by imidization At least one polymer selected from the group consisting of polyimine.

(XA、XC各自獨立表示經由熱而被氫原子所取代之保護基。XB表示單鍵或碳數1~40之有機基，此時，酯基(-COO-基)所鍵結之原子為碳原子)。 (X A and X C each independently represent a protecting group substituted by a hydrogen atom via heat. X B represents a single bond or an organic group having 1 to 40 carbon atoms, and at this time, an ester group (-COO- group) is bonded. The atom is a carbon atom).

(B)成份：含有式(B-1)之四羧酸二酐的四羧酸成 份，與含有式(B-2)之二胺的二胺成份所得之聚醯胺酸。 (B) Ingredients: tetracarboxylic acid containing tetracarboxylic dianhydride of formula (B-1) And a poly-proline which is obtained from a diamine component containing a diamine of the formula (B-2).

(Y1為具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種類的結構之2價之有機基。B1及B2各自獨立表示、氫原子、可具有取代基之碳數1~10之烷基等)。 (Y 1 is a divalent organic group having at least one type of structure selected from the group consisting of an amine group, an imido group, and a nitrogen-containing heterocyclic ring. B 1 and B 2 each independently represent a hydrogen atom; An alkyl group having a carbon number of 1 to 10 having a substituent, etc.).

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，有關液晶配向劑、由此液晶配向劑所得之液晶配向膜，及具備此液晶配向膜之液晶顯示元件的發明。 The present invention relates to a liquid crystal alignment agent obtained from a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element comprising the liquid crystal alignment film.

液晶電視、液晶顯示器等所使用的液晶顯示元件，通常，於元件內設置控制液晶配列(亦稱為配向)狀態之液晶配向膜。 In a liquid crystal display device used for a liquid crystal television or a liquid crystal display, a liquid crystal alignment film for controlling a liquid crystal alignment (also referred to as alignment) is usually provided in the device.

現在，工業上最最普及的液晶配向膜，一般為對形成於電極基板上之聚醯亞胺前驅物，例如，聚醯胺酸(亦稱為聚醯胺酸)或聚醯胺酸酯，於該些經醯亞胺化之聚醯亞胺等所形成的樹脂被膜表面，使用綿、尼龍、聚酯等布向一方向摩擦，即進行所謂摩擦處理法之方式而製得。 Nowadays, the most popular liquid crystal alignment film in the industry is generally a polyimide precursor formed on an electrode substrate, for example, poly-proline (also known as poly-proline) or polyphthalate. The surface of the resin film formed by the yttrium imidized polyimine or the like is obtained by rubbing in a direction using a cloth such as cotton, nylon or polyester, that is, a so-called rubbing treatment method.

控制液晶配向膜的配向狀態之步驟(亦稱為液晶配向處理方法)中，對樹脂被膜表面進行摩擦處理之方法，因簡便且具有優良生產性，故為工業上極有用的方法。但是，隨著對於液晶顯示元件之高性能化、高精細化及大型化之要求日益增加，伴隨摩擦處理會產生液晶配向膜表面 之傷痕、塵埃、機械性力或靜電等影響，甚至，配向處理之面內不均勻性等各種問題則日漸明朗化。 In the step of controlling the alignment state of the liquid crystal alignment film (also referred to as a liquid crystal alignment treatment method), the method of rubbing the surface of the resin film is industrially extremely useful because it is simple and has excellent productivity. However, as the requirements for high performance, high definition, and large size of liquid crystal display elements are increasing, the surface of the liquid crystal alignment film is generated along with the rubbing treatment. Various problems such as flaws, dust, mechanical force or static electricity, and even in-plane unevenness of the alignment treatment are becoming more and more clear.

取代摩擦處理法之方法，已知例如經由照射偏光紫外線之方式，以控制液晶的配向狀態之光配向處理。利用光配向處理的液晶配向處理法，於作用機制上，已有提出利用光異性化反應者、利用光交聯反應者，甚至利用光分解反應者等提案(非專利文獻1所示)。 Instead of the method of the rubbing treatment method, it is known to control the photoalignment treatment of the alignment state of the liquid crystal by, for example, irradiating the polarized ultraviolet rays. In the liquid crystal alignment treatment method using the photo-alignment treatment, it has been proposed to use a photo-analytical reaction, a photo-crosslinking reaction, or even a photo-decomposition reactor (Non-Patent Document 1).

又，專利文獻1中，則有提出主鏈具有環丁烷環等脂環結構的聚醯亞胺系樹脂所形成之樹脂被膜，被使用於光配向處理之提案。特別是，聚醯亞胺系樹脂於被使用作為光配向法中之液晶配向膜之情形，與其他樹脂者相比較時，因具有更高耐熱性，故其實用性受到極大之期待。 Further, in Patent Document 1, a resin film formed of a polyimide resin having a condensed ring structure such as a cyclobutane ring in its main chain is proposed, and it is proposed to be used for optical alignment treatment. In particular, when a polyimine-based resin is used as a liquid crystal alignment film in a photo-alignment method, it has a high heat resistance when compared with other resins, and thus its practicality is greatly expected.

上述光配向處理中，無需摩擦之液晶配向處理，具有於工業上亦可以簡便的製造製程予以生產之優點。此外，IPS(In-Plane Switching)驅動方式或FFS(Fringe Field Switching)驅動方式的液晶顯示元件中，使用前述光配向處理所得之液晶配向膜，與摩擦處理法所得之液晶配向膜相比較時，就可期待提高液晶顯示元件之反差或提高視角特性等觀點，而可使液晶顯示元件之性能向上提升。因此，光配向處理法，於今後的液晶配向處理方法中，為特別受到注目者。 In the above optical alignment treatment, there is no need for rubbing liquid crystal alignment treatment, and there is an advantage that it can be produced in an industrially simple manufacturing process. Further, in the liquid crystal display device of the IPS (In-Plane Switching) driving method or the FFS (Fringe Field Switching) driving method, when the liquid crystal alignment film obtained by the above-described photoalignment treatment is used, compared with the liquid crystal alignment film obtained by the rubbing treatment method, It is expected that the contrast of the liquid crystal display element can be improved or the viewing angle characteristics can be improved, and the performance of the liquid crystal display element can be improved. Therefore, the optical alignment treatment method is particularly attracting attention in the future liquid crystal alignment processing method.

另一方面，IPS驅動方式或FFS驅動方式的液晶顯示元件所使用的液晶配向膜，除優良的液晶配向性或電氣特性等基本特性以外，尚必須具有可抑制經長時間之 交流驅動，液晶無法回復初期配向之狀態所發生之殘像(以下，亦稱為交流驅動造成之殘像)，且可提早緩和因直流電壓所蓄積之殘留電荷等特性。 On the other hand, the liquid crystal alignment film used for the liquid crystal display device of the IPS driving method or the FFS driving method must have a long-term property in addition to excellent liquid crystal alignment properties or electrical characteristics. In the AC drive, the liquid crystal cannot recover the afterimage generated by the initial alignment (hereinafter, also referred to as the afterimage caused by the AC drive), and the characteristics such as the residual charge accumulated by the DC voltage can be relaxed early.

聚醯亞胺系之液晶配向膜中，為配合上述之要求，而有各種的提案。例如，作為可縮短直流電壓所造成之殘像消失為止的時間的液晶配向膜，除聚醯胺酸或含醯亞胺基之聚醯胺酸以外，尚使用含有特定結構的三級胺的液晶配向劑者、使用具有吡啶骨架等的特定原料的含可溶性聚醯亞胺的液晶配向劑者等提案(例如，專利文獻2及3所示)。 In the polyimine-based liquid crystal alignment film, various proposals have been made to meet the above requirements. For example, as a liquid crystal alignment film capable of shortening the time until the afterimage of the DC voltage is lost, a liquid crystal containing a tertiary amine having a specific structure is used in addition to polyphosphonic acid or a polyamido acid containing a quinone imine group. A liquid crystal alignment agent containing a soluble polyimine having a specific raw material such as a pyridine skeleton is used as an alignment agent (for example, Patent Documents 2 and 3).

又，作為具有高電壓保持率、可縮短直流電壓所造成之殘像消失為止的時間的液晶配向膜者，亦有提出一種除聚醯胺酸或其醯亞胺化聚合物等以外，尚含有極少量之由分子內含有1個羧酸基之化合物、分子內含有1個羧酸酐基之化合物，及分子內含有1個三級胺基之化合物所選出之化合物的液晶配向劑之提案(例如，專利文獻4所示)。 Further, as a liquid crystal alignment film having a high voltage holding ratio and a time period in which the residual image due to a DC voltage can be shortened, it is also proposed to contain, in addition to poly-proline or a ruthenium imidized polymer thereof, A proposal for a liquid crystal alignment agent containing a compound having one carboxylic acid group in the molecule, a compound having one carboxylic acid anhydride group in the molecule, and a compound selected from a compound having one tertiary amino group in the molecule (for example) , Patent Document 4).

又，具有優良液晶配向性、高電壓保持率、較少之殘像、優良信賴性，且顯示高預傾角的液晶配向膜，已知例如可使用將特定結構之四羧酸二酐與具有環丁烷之四羧酸二酐經特定所製得之聚醯胺酸，或含有該醯亞胺化聚合物的液晶配向劑者(例如，專利文獻5所示)。 Further, a liquid crystal alignment film having excellent liquid crystal alignment, high voltage retention, less afterimage, and excellent reliability and exhibiting a high pretilt angle is known, for example, a tetracarboxylic dianhydride having a specific structure and having a ring The tetracarboxylic dianhydride of butane is specifically obtained by a polyamic acid or a liquid crystal alignment agent containing the ruthenium iodide polymer (for example, Patent Document 5).

此外，橫電場驅動方式的液晶顯示元件中，對於抑制因產生的交流驅動所造成之殘像的方法，已有提 出使用液晶配向性為良好，且液晶分子相互作用更大之特定液晶配向膜的方法之提案(專利文獻6所示)。 Further, in the liquid crystal display device of the horizontal electric field drive method, a method for suppressing the afterimage caused by the generated AC drive has been proposed. A proposal for a method of using a specific liquid crystal alignment film having a good liquid crystal alignment property and having a large interaction of liquid crystal molecules (Patent Document 6).

又，IPS驅動方式或FFS驅動方式的液晶晶胞，靜電容易蓄積於液晶晶胞內，於施加經由驅動所生成之非對稱電壓時，液晶晶胞內也會蓄積電荷，該些之蓄積之電荷將會擾亂液晶之配向，或會造成殘像或殘影而影響顯示，使得液晶元件之顯示品質顯著降低。於該狀態下再度通電之情形，於初期段階中，液晶分子將無法進行良好的控制，而會生成閃爍(FLICKER)等現象。特別是IPS驅動方式或FFS驅動方式中，相較於縱電場方式，畫素電極與共通電極之距離將更為接近，而配向膜或液晶層受到強力電場之作用，將會更容易顯現出該些不適當狀態等問題點。 Further, in the liquid crystal cell of the IPS driving method or the FFS driving method, static electricity is easily accumulated in the liquid crystal cell, and when an asymmetric voltage generated by driving is applied, charges are accumulated in the liquid crystal cell, and the accumulated charges are accumulated. The alignment of the liquid crystal will be disturbed, or the afterimage or afterimage may be caused to affect the display, so that the display quality of the liquid crystal element is remarkably lowered. In the case where the power is again applied in this state, in the initial stage, the liquid crystal molecules cannot be well controlled, and a phenomenon such as flicker (FLICKER) is generated. In particular, in the IPS driving mode or the FFS driving mode, the distance between the pixel electrode and the common electrode is closer than that of the vertical electric field mode, and the alignment film or the liquid crystal layer is subjected to a strong electric field, which is more likely to appear. Some problems such as inappropriate status.

解決因上述交流驅動之非對稱化所造成之電荷蓄積之方法，例如，已有提出由電極上所形成的第1配向膜，與該表面上所形成之由苯均四酸二酐與二胺所形成之聚合物，且，具有由電阻低於第1配向膜的第2配向膜所形成之液晶配向膜的液晶顯示裝置，其可抑制因交流驅動的非對稱化所造成之電荷蓄積，且，可提早緩和所蓄積之電荷等報告(例如，專利文獻7所示)。 A method for solving the charge accumulation caused by the asymmetry of the above-described AC drive, for example, a first alignment film formed on an electrode and a pyromellitic dianhydride and a diamine formed on the surface have been proposed. a liquid crystal display device having a liquid crystal alignment film formed of a second alignment film having a lower electric resistance than the first alignment film, which suppresses charge accumulation due to asymmetry of AC driving, and The report of the accumulated electric charge can be relaxed early (for example, as shown in Patent Document 7).

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

[專利文獻1]日本特開平9-297313號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-297313

[專利文獻2]日本特開平9-316200號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 9-316200

[專利文獻3]日本特開平10-104633號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 10-104633

[專利文獻4]日本特開平8-76128號公報 [Patent Document 4] Japanese Patent Laid-Open No. Hei 8-76128

[專利文獻5]日本特開平9-138414號公報 [Patent Document 5] Japanese Patent Laid-Open No. Hei 9-138414

[專利文獻6]日本特開平11-38415號公報 [Patent Document 6] Japanese Patent Laid-Open No. Hei 11-38415

[專利文獻7]日本特開2013-167782號公報 [Patent Document 7] Japanese Laid-Open Patent Publication No. 2013-167782

[非專利文獻] [Non-patent literature]

[非專利文獻1]「液晶光配向膜」木戸脇、市村 機能材料1997年11月號、Vol.17 No.11 13-22頁 [Non-Patent Document 1] "Liquid Crystal Light Alignment Film", Miki-shi, Shimura, Functional Materials, November 1997, Vol.17 No.11 13-22

本發明者們，對於製得一種抑制IPS驅動方式或FFS驅動方式的液晶顯示元件中所發生之因交流驅動的非對稱化所造成之電荷蓄積、提早緩和因直流電壓所蓄積之殘留電荷，甚至抑制因交流驅動所造成之殘像的液晶配向膜之方法，而著眼於一種摻雜具有優良液晶配向性、強大液晶配向規制力之成份(I)，與兼具抑制因交流驅動的非對稱化所造成之電荷蓄積，與提早緩和因直流電壓所蓄積之殘留電荷之成份(II)所得之液晶配向劑。但是，該液晶配向劑，特別是於光配向處理法中，也並非可解決上述問題者。 The inventors of the present invention have accumulated charge accumulation due to asymmetry of AC driving occurring in a liquid crystal display device which suppresses an IPS driving method or an FFS driving method, and prematurely alleviate residual charges accumulated by a DC voltage, and even A method for suppressing a liquid crystal alignment film of an afterimage caused by an AC drive, and focusing on a component (I) having an excellent liquid crystal alignment property and a strong liquid crystal alignment regulation, and asymmetry of a combination of suppression and AC driving The liquid crystal alignment agent obtained by accumulating the charge and prematurely alleviating the component (II) of the residual charge accumulated by the DC voltage. However, the liquid crystal alignment agent, particularly in the photoalignment treatment method, does not solve the above problems.

即，由含有上述2個成份之液晶配向劑所得之液晶配 向膜，因存在成份(II)，雖兼具可抑制因交流驅動的非對稱化所造成之電荷蓄積與提早緩和因直流電壓所蓄積之殘留電荷，但會連帶造成液晶配向規制力之阻礙，使得液晶配向安定性不足，會產生交流驅動所造成之殘像，因此，並非可滿足該些全部之特性。 That is, the liquid crystal matching obtained from the liquid crystal alignment agent containing the above two components In the film, because of the presence of the component (II), the charge accumulation due to the asymmetry of the AC drive can be suppressed and the residual charge accumulated by the DC voltage can be relieved early, but the liquid crystal alignment regulation force is hindered. The liquid crystal alignment stability is insufficient, and the afterimage caused by the AC drive is generated, and therefore, all of the characteristics are not satisfied.

本發明為提供一種摻雜有具有優良液晶配向性、液晶配向規制力，高液晶配向安定性成份，兼具有可抑制因交流驅動的非對稱化所造成之電荷蓄積與提早緩和因直流電壓所蓄積之殘留電荷之成份的液晶配向劑，其可抑制因交流驅動的非對稱化所造成之電荷蓄積、提早緩和因直流電壓所蓄積之殘留電荷，且可抑制因交流驅動所造成之殘像的液晶配向膜為目的。 The invention provides a doping with excellent liquid crystal alignment property, liquid crystal alignment regulation force, high liquid crystal alignment stability component, and has the ability to suppress charge accumulation and early relaxation due to AC drive asymmetry due to DC voltage. A liquid crystal alignment agent which accumulates a component of a residual charge, which suppresses charge accumulation due to asymmetry of AC driving, prematurely alleviates residual charges accumulated by a DC voltage, and suppresses afterimage caused by AC driving. The liquid crystal alignment film is for the purpose.

此外，並提供一種具有上述液晶配向膜的液晶顯示元件及可提供作為上述液晶配向膜之液晶配向劑。 Further, a liquid crystal display element having the above liquid crystal alignment film and a liquid crystal alignment agent which can provide the liquid crystal alignment film are provided.

本發明者們，經深入研究結果，發現具有含有特定結構之聚合物的液晶配向劑對於達成上述目的極為有效，因而完成本發明。 The inventors of the present invention have found that a liquid crystal alignment agent having a polymer having a specific structure is extremely effective for achieving the above object, and thus completed the present invention.

即、本發明為具有以下主要內容者。 That is, the present invention is the one having the following main contents.

1.一種液晶配向劑，其特徵為，含有下述(A)成份，及(B)成份，(A)成份：具有由下述式[1A]及[1B]所成之群所選出之至少1種的結構之聚醯亞胺前驅物，及該聚醯亞胺前 驅物經醯亞胺化所得之聚醯亞胺所成之群所選出之至少1種的聚合物。 A liquid crystal alignment agent comprising the following (A) component and (B) component, (A) component: having at least one selected from the group consisting of the following formulas [1A] and [1B] a structure of a polyimine precursor, and the pre-polyimine At least one polymer selected from the group consisting of polyimine obtained by imidization of hydrazine.

(XA及XC各自獨立表示經由熱而被氫原子所取代之保護基。XB表示單鍵或碳數1~40之有機基，此時，酯基(-COO-基)所鍵結之原子為碳原子)。 (X A and X C each independently represent a protecting group substituted by a hydrogen atom via heat. X B represents a single bond or an organic group having 1 to 40 carbon atoms, and at this time, an ester group (-COO- group) is bonded. The atom is a carbon atom).

(B)成份：下述含有式(B-1)之四羧酸二酐的四羧酸成份，與由下述含有式(B-2)之二胺的二胺成份經聚縮合反應所得之聚醯胺酸及該聚醯亞胺前驅物經醯亞胺化所得之聚醯亞胺所成之群所選出之至少1種的聚合物。 (B) Component: The following tetracarboxylic acid component containing a tetracarboxylic dianhydride of the formula (B-1), which is obtained by polycondensation reaction with a diamine component containing the diamine of the formula (B-2) below At least one polymer selected from the group consisting of polylysine and the polyimine precursor obtained by the ruthenium imidization.

(式中，Y1為具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種類的結構之2價之有機基。B1及B2各自獨立表示、氫原子、碳數1~10之烷基、碳數1~10之烯基，或碳數1~10之炔基，該些之基可具有取代基)。 (wherein Y 1 is a divalent organic group having at least one type of structure selected from the group consisting of an amine group, an imido group, and a nitrogen-containing heterocyclic ring. B 1 and B 2 each independently represent hydrogen. The atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms may have a substituent.

2.如上述1之液晶配向劑，其中，由前述式[1A]及[1B]所成之群所選出之至少1種之結構為下述式[1a]、式[1b]或式[1c]之結構。 2. The liquid crystal alignment agent according to the above 1, wherein at least one selected from the group consisting of the above formulas [1A] and [1B] has the following formula [1a], formula [1b] or formula [1c] The structure of].

(式[1a]中，Xa中，m為1之情形，表示氫原子或碳數1~20之有機基。Xb表示經由熱而被氫原子所取代之保護基。m表示1或2之整數。但，m為2之情形中，Xa不具有取代基。式[1b]中，Xc表示經由熱而被氫原子所取代之保護基。式[1c]中，Xd表示單鍵或碳數1~20之有機基，Xe表示氫原子或碳數1~20之有機基，Xf表示經由熱而被氫原子所取代之保護基，n表示1~4之整數)。 (In the formula [1a], in the case of X a , when m is 1, it represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. X b represents a protecting group substituted by a hydrogen atom via heat. m represents 1 or 2 In the case where m is 2, X a does not have a substituent. In the formula [1b], X c represents a protecting group substituted by a hydrogen atom via heat. In the formula [1c], X d represents a single A bond or an organic group having 1 to 20 carbon atoms, X e represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X f represents a protecting group substituted by a hydrogen atom via heat, and n represents an integer of 1 to 4).

3.如上述2記載之液晶配向劑，其中，前述(A)成份為，由含有具有前述式[1a]、式[1b]及式[1c]所示結構所選出之至少1種之結構的二胺之二胺成份與四羧酸成份經聚縮合而得之聚醯亞胺前驅物及該聚醯亞胺前驅物經醯亞胺而得之聚醯亞胺所選出之至少一種的聚合物。 3. The liquid crystal alignment agent according to the above 2, wherein the component (A) is at least one selected from the group consisting of the structures represented by the above formula [1a], the formula [1b], and the formula [1c]. a polydiimide precursor obtained by polycondensation of a diamine diamine component and a tetracarboxylic acid component, and a polymer obtained from at least one selected from the group consisting of a polyimide and a polyimide derivative. .

4.如上述3記載之液晶配向劑，其中，前述二胺為下述式[1-1]所示之二胺。 4. The liquid crystal alignment agent according to the above 3, wherein the diamine is a diamine represented by the following formula [1-1].

(式中，XD表示具有由前述式[1a]、式[1b]及式[1c]所成之群所選出之至少1種之結構的碳數5~50之有機基，A1及A2各自獨立表示氫原子、碳數1~10之烷基、碳數1~10之烯基，或碳數1~10之炔基，該些之基可具有取 代基)。 (wherein X D represents an organic group having 5 to 50 carbon atoms having a structure selected from the group consisting of the above formula [1a], formula [1b], and formula [1c], and A 1 and A 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, and these groups may have a substituent).

5.如上述4記載之液晶配向劑，其中，前述二胺為由下述式[1a-1]~式[1c-1]所成之群所選出之至少1種的二胺。 5. The liquid crystal alignment agent according to the above-mentioned item 4, wherein the diamine is at least one selected from the group consisting of the following formulas [1a-1] to [1c-1].

(式[1a-1]中，X1表示由單鍵、碳數1~10之伸烷基、-O-、-N(R1)-、-CON(R2)-、-N(R3)CO-、-CH2O-、-COO-及-OCO-所選出之至少1種的有機基。但，R1、R2及R3各自獨立表示氫原子或碳數1~3之烷基。X2表示單鍵或碳數1~10之伸烷基。Xa中，m為1之情形，表示氫原子或碳數1~20之有機基。Xb表示經由熱而被氫原子所取代之保護基。m表示1或2之整數，此時，m為2之情形，Xa不具有取代基。p表示1~4之整數，q表示1~4之整數。 (In the formula [1a-1], X 1 represents a single bond, an alkyl group having 1 to 10 carbon atoms, -O-, -N(R 1 )-, -CON(R 2 )-, -N(R). 3 ) at least one organic group selected from CO-, -CH 2 O-, -COO-, and -OCO-. However, R 1 , R 2 and R 3 each independently represent a hydrogen atom or a carbon number of 1 to 3. Alkyl group. X 2 represents a single bond or an alkylene group having 1 to 10 carbon atoms. In the case of X a , when m is 1, it represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. X b represents hydrogen by heat. The protecting group substituted by an atom. m represents an integer of 1 or 2. In the case where m is 2, X a does not have a substituent. p represents an integer of 1 to 4, and q represents an integer of 1 to 4.

式[1b-1]中，X3及X7各自獨立表示由單鍵、碳數1~ 10之伸烷基、-O-、-N(R1)-、-CON(R2)-、-N(R3)CO-、-CH2O-、-COO-及-OCO-所選出之至少1種。又，R1、R2及R3各自獨立表示氫原子或碳數1~3之烷基。X4及X6各自獨立表示單鍵或碳數1~10之伸烷基，X5表示單鍵或碳數1~10之伸烷基，Xc表示經由熱而被氫原子所取代之保護基，r表示1~4之整數。 In the formula [1b-1], X 3 and X 7 each independently represent a single bond, an alkyl group having 1 to 10 carbon atoms, -O-, -N(R 1 )-, -CON(R 2 )-, At least one selected from the group consisting of -N(R 3 )CO-, -CH 2 O-, -COO-, and -OCO-. Further, R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X 4 and X 6 each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms, X 5 represents a single bond or an alkylene group having 1 to 10 carbon atoms, and X c represents a protection by substitution of a hydrogen atom via heat. Base, r represents an integer from 1 to 4.

式[1c-1]中，X8表示由單鍵、碳數1~10之伸烷基、-O-、-N(R1)-、-CON(R2)-、-N(R3)CO-、-CH2O-、-COO-及-OCO-所選出之至少1種。又，R1、R2及R3各自獨立表示氫原子或碳數1~3之烷基。X9表示單鍵或碳數1~10之伸烷基，Xd表示單鍵或碳數1~20之有機基，Xe表示氫原子或碳數1~20之有機基，Xf表示經由熱而被氫原子所取代之保護基，n表示1~4之整數，s表示1~4之整數，t表示1~4之整數，式[1a-1]~式[1c-1]中，A1~A6各自獨立表示氫原子、碳數1~10之烷基、碳數1~10之烯基，或碳數1~10之炔基，該些之基可具有取代基)。 In the formula [1c-1], X 8 represents a single bond, an alkyl group having 1 to 10 carbon atoms, -O-, -N(R 1 )-, -CON(R 2 )-, -N(R 3 At least one selected from the group consisting of CO-, -CH 2 O-, -COO-, and -OCO-. Further, R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X 9 represents a single bond or an alkylene group having 1 to 10 carbon atoms, X d represents a single bond or an organic group having 1 to 20 carbon atoms, and X e represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and X f represents via a protecting group which is substituted by a hydrogen atom, n represents an integer of 1 to 4, s represents an integer of 1 to 4, and t represents an integer of 1 to 4, in the formula [1a-1] to the formula [1c-1], A 1 to A 6 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, and these groups may have a substituent).

6.如上述5記載之液晶配向劑，其中，前述二胺為由下述式[1d-1]~式[1d-5]所成之群所選出之至少1種的二胺。 6. The liquid crystal alignment agent according to the above-mentioned item 5, wherein the diamine is at least one selected from the group consisting of the following formulas [1d-1] to [1d-5].

(式[1d-1]~式[1d-5]中，R1~R7各自獨立表示由下述式[a-1]~式[a-6]所成之群所選出之至少1種之結構，A1~A10各自獨立表示氫原子、碳數1~10之烷基、碳數1~10之烯基，或碳數1~10之炔基，該些之基可具有取代基)。 (In the formula [1d-1] to the formula [1d-5], R 1 to R 7 each independently represent at least one selected from the group consisting of the following formulas [a-1] to [a-6]. In the structure, A 1 to A 10 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, and these groups may have a substituent. ).

(式[a-2]中，R1表示碳數1~5之烷基)。 (In the formula [a-2], R 1 represents an alkyl group having 1 to 5 carbon atoms).

7.如上述1~6之任一者所記載的液晶配向劑，其中，前述(A)成份之聚合物為，由含有下述式[3-1]所表示之二胺的二胺成份與四羧酸成份經聚縮合而得之聚醯亞胺前驅物及該聚醯亞胺前驅物經醯亞胺化所得之聚醯亞胺所成之群所選出之至少1種。 7. The liquid crystal alignment agent according to any one of the above-mentioned items (1), wherein the polymer of the component (A) is a diamine component containing a diamine represented by the following formula [3-1]. At least one selected from the group consisting of a polycondensed imide precursor obtained by polycondensation of a tetracarboxylic acid component and a polyimine imide obtained by hydrazylation of the polyiminoimine precursor.

(式[3-1]中，XE表示由下述式[3a-1]~式[3a-10]所成之群所選出之至少1種之結構，A1及A2各自獨立表示氫原子、碳數1~10之烷基、碳數1~10之烯基，或碳數1~10之炔基，該些之基可具有取代基)。 (In the formula [3-1], X E represents a structure selected from at least one selected from the group consisting of the following formula [3a-1] to the formula [3a-10], and A 1 and A 2 each independently represent hydrogen. The atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms may have a substituent.

(式[3a-9]中，n表示1~5之整數)。 (in the formula [3a-9], n represents an integer of 1 to 5).

8.如上述1~7之任一者所記載的液晶配向劑，其中，前述四羧酸成份為下述式[4]所表示之四羧酸二酐。 8. The liquid crystal alignment agent according to any one of the above-mentioned, wherein the tetracarboxylic acid component is a tetracarboxylic dianhydride represented by the following formula [4].

(Z表示由下述式[4a]~[4q]所成之群所選出之至少1種之結構)。 (Z represents a structure of at least one selected from the group consisting of the following formulas [4a] to [4q]).

(式[4a]中，Z1~Z4各自獨立表示氫原子、甲基、乙基、丙基、氯原子或苯環，式[4g]中，Z5及Z6各自獨立表示氫原子或甲基)。 (In the formula [4a], Z 1 to Z 4 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, and in the formula [4g], Z 5 and Z 6 each independently represent a hydrogen atom or methyl).

9.如上述8記載之液晶配向劑，其中，前述四羧酸成份為，前述式[4]中之Z為由前述式[4a]、式[4e]~式[4g]、式[4l]、式[4m]或式[4p]所成之群所選出之至少1種的四羧酸化合物。 9. The liquid crystal alignment agent according to the above 8, wherein the tetracarboxylic acid component is such that Z in the above formula [4] is represented by the above formula [4a], formula [4e] to formula [4g], and formula [4l]. At least one tetracarboxylic acid compound selected from the group consisting of the formula [4m] or the formula [4p].

10.如上述5~9之任一者所記載的液晶配向劑，其 中，前述(A)成份之聚合物中，前述式[1a-1]、式[1b-1]及式[1c-1]所示之二胺，於全二胺成份100莫耳%中，為5~30莫耳%。 10. The liquid crystal alignment agent according to any one of the above 5 to 9, which In the polymer of the component (A), the diamine represented by the above formula [1a-1], the formula [1b-1] and the formula [1c-1] is contained in 100% by mole of the total diamine component. It is 5~30% by mole.

11.如上述1~10之任一者所記載的液晶配向劑，其中，前述(B)成份中，前述式(B-1)所表示之四羧酸二酐，相對於全四羧酸成份1莫耳，為10~100莫耳%。 The liquid crystal alignment agent according to any one of the above-mentioned items (1), wherein the tetracarboxylic dianhydride represented by the formula (B-1) is a component of the tetracarboxylic acid component. 1 mole, 10% to 100%.

12.如上述1~11之任一者所記載的液晶配向劑，其中，前述(B)成份中，前述式(B-2)之二胺，相對於全二胺成份1莫耳，為10~100莫耳%。 The liquid crystal alignment agent according to any one of the above-mentioned items (1), wherein the diamine of the formula (B-2) is 10 per mol of the total diamine component. ~100% by mole.

13.如上述1~12之任一者所記載的液晶配向劑，其中，前述式(B-2)中之Y1為由具有下述式(YD-1)~式(YD-5)所表示之氮原子的2價之有機基所成之群所選出之至少1種。 The liquid crystal alignment agent according to any one of the above-mentioned formula (B-2), wherein Y 1 in the formula (B-2) has the following formula (YD-1) to (YD-5) At least one selected from the group consisting of divalent organic groups of the nitrogen atom.

(式(YD-1)中，E1為碳數3~15之含氮原子之雜環，Q1為氫原子，或可具有取代基之素數1~20之烴基。式(YD-2)中，W1為碳數1~10之烴基，E2為具有含氮原子之雜環的碳數3~15之1價之有機基，或被碳數1~6 之脂肪族基所取代的二取代胺基。式(YD-3)中，W2為碳數6~15，且具有1~2個苯環之2價之有機基，W3為碳數2~5之伸烷基或伸聯苯基，Q2為氫原子、碳數1~5之烷基，或苯環。a為0~1之整數。式(YD-4)中，E3為碳數3~15之含氮原子之雜環。式(YD-5)中，E4為碳數3~15之含氮原子之雜環，W5為碳數2~5之伸烷基)。 (In the formula (YD-1), E 1 is a heterocyclic ring containing a nitrogen atom having 3 to 15 carbon atoms, and Q 1 is a hydrogen atom or a hydrocarbon group having a substituent of 1 to 20 which may have a substituent. In the above, W 1 is a hydrocarbon group having 1 to 10 carbon atoms, and E 2 is a monovalent organic group having a carbon number of 3 to 15 having a hetero ring containing a nitrogen atom, or is substituted with an aliphatic group having 1 to 6 carbon atoms. The disubstituted amine group. In the formula (YD-3), W 2 is a carbon number of 6 to 15, and has a divalent organic group of 1 to 2 benzene rings, and W 3 is a C 2 to 5 alkyl group. Or a biphenyl group, Q 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a benzene ring. a is an integer of 0 to 1. In the formula (YD-4), E 3 is a carbon number of 3 to 15. A heterocyclic ring containing a nitrogen atom. In the formula (YD-5), E 4 is a heterocyclic ring containing a nitrogen atom having 3 to 15 carbon atoms, and W 5 is an alkylene group having 2 to 5 carbon atoms.

14.如上述1~13之任一者所記載的液晶配向劑，其中，前述式(YD-1)、式(YD-2)、式(YD-4)，及式(YD-5)記載之E1、E2、E3、及E4之碳數3~15之含氮原子之雜環，為由吡咯、吡咯、咪唑、吡唑、噁唑、噻唑、哌啶、哌、吡啶、吡、吲哚、苯併咪唑、喹啉，及異喹啉所成之群所選出之至少1種。 14. The liquid crystal alignment agent according to any one of the above-mentioned formulas (1D-1), (YD-2), (YD-4), and (YD-5). a heterocyclic ring containing a nitrogen atom of 3 to 15 carbon atoms of E 1 , E 2 , E 3 , and E 4 , pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine Pyridine, pyridyl At least one selected from the group consisting of hydrazine, benzimidazole, quinoline, and isoquinoline.

15.如上述1~14之任一者所記載的液晶配向劑，其中，前述式(B-2)之Y1為由具有下述式(YD-6)~式(YD-21)所表示之氮原子的2價之有機基所成之群所選出之至少1種。 The liquid crystal alignment agent of the above formula (B-2), wherein Y 1 of the above formula (B-2) is represented by the following formula (YD-6) to formula (YD-21) At least one selected from the group consisting of divalent organic groups of nitrogen atoms.

(式(YD-17)中，h為1~3之整數，式(YD-14)及式(YD-21)中，j為0~3之整數)。 (In the formula (YD-17), h is an integer from 1 to 3, and in the formula (YD-14) and the formula (YD-21), j is an integer from 0 to 3).

16.如上述15記載之液晶配向劑，其中，前述式(B-2)之Y1為由具有前述式(YD-14)及式(YD-18)所表示之氮原子的2價之有機基所成之群所選出之至少1種。 16. The liquid crystal alignment agent according to the above formula (B-2), wherein Y 1 of the formula (B-2) is a divalent organic compound having a nitrogen atom represented by the above formula (YD-14) and formula (YD-18). At least one selected from the group.

17.如上述1~16之任一者所記載的液晶配向劑，其中，前述(B)成份之聚合物，相對於前述(A)成份之聚合物100質量份，為40~250質量份。 The liquid crystal alignment agent according to any one of the above-mentioned items (1), wherein the polymer of the component (B) is 40 to 250 parts by mass based on 100 parts by mass of the polymer of the component (A).

18.如上述1~17之任一者所記載的液晶配向劑，其為含有由N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮及γ-丁內酯所成之群所選出之至少1種的溶劑。 18. The liquid crystal alignment agent according to any one of 1 to 17, which comprises N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone. At least one solvent selected from the group.

19.如上述1~18之任一者所記載的液晶配向劑，其 為含有由1-己醇、環己醇、1,2-乙烷二醇、1,2-丙烷二醇、丙二醇單丁基醚、乙二醇單丁基醚及二丙二醇二甲基醚所成之群所選出之至少1種的溶劑。 19. The liquid crystal alignment agent according to any one of the above 1 to 18, wherein Containing 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether At least one solvent selected from the group.

20.如上述1~19之任一者所記載的液晶配向劑，其為含有由，具有環氧基、異氰酸酯基、環氧丙烷基或環碳酸酯基之交聯性化合物、具有由羥基、羥烷基或低級烷氧基烷基所成之群所選出之至少1種的取代基之交聯性化合物，及具有聚合性不飽和鍵結之交聯性化合物所成之群所選出之至少1種。 The liquid crystal alignment agent according to any one of the above 1 to 19, which contains a crosslinkable compound having an epoxy group, an isocyanate group, an oxypropylene group or a cyclic carbonate group, and has a hydroxyl group. a crosslinkable compound of at least one substituent selected from the group consisting of a hydroxyalkyl group or a lower alkoxyalkyl group, and at least a group selected from the group of crosslinkable compounds having a polymerizable unsaturated bond 1 species.

21.一種液晶配向膜，其特徵為，塗佈上述1~20之任一者所記載的液晶配向劑，並經燒結而製得。 A liquid crystal alignment film obtained by applying the liquid crystal alignment agent described in any one of the above 1 to 20 and sintering it.

22.一種液晶配向膜，其特徵為，使用上述1~20之任一者所記載的液晶配向劑，並依噴墨法而製得。 A liquid crystal alignment film obtained by using the liquid crystal alignment agent described in any one of the above 1 to 20, which is obtained by an inkjet method.

23.一種整液晶配向膜，其特徵為，於上述21或22記載之液晶配向膜上，照射偏光之輻射線而製得。 A liquid crystal alignment film obtained by irradiating a polarized radiation on the liquid crystal alignment film described in the above 21 or 22.

24.一種液晶顯示元件，其特徵為，具有上述21~23之任一者所記載的液晶配向膜。 A liquid crystal display device comprising the liquid crystal alignment film according to any one of the above 21 to 23.

本發明之含有2種類的具有特定結構之聚醯亞胺前驅物或聚醯亞胺所選出之至少1種的聚合物之液晶配向劑，可形成一可抑制因交流驅動的非對稱化所造成之電荷蓄積、提早緩和因直流電壓所蓄積之殘留電荷，此外也可抑制因交流驅動所造成之殘像的液晶配向膜。特別 是，適合作為照射偏光輻射線的光配向處理法使用之液晶配向膜。 The liquid crystal alignment agent of the present invention containing two kinds of polymers having a specific structure of a polyimine imine precursor or at least one selected from the group consisting of polyimine can form an antisymmetry caused by AC driving. The charge is accumulated, the residual charge accumulated by the DC voltage is relaxed early, and the liquid crystal alignment film due to the residual image caused by the AC drive can be suppressed. particular Yes, it is suitable as a liquid crystal alignment film used for the photoalignment processing method which irradiates a polarizing radiation.

又，具有由本發明之液晶配向劑所得之液晶配向膜的液晶顯示元件，為具有優良信賴性者，而適合使用於大畫面且高精細度之液晶電視，或中小型之導航系統、智慧型手機等。 Further, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention is excellent in reliability, and is suitable for use in a large-screen and high-definition liquid crystal television, or a small-sized navigation system or a smart phone. Wait.

[實施發明之形態] [Formation of the Invention] <特定結構(1A)及特定結構(1B)> <Specific structure (1A) and specific structure (1B)>

本發明之(A)成份(以下，亦稱為特定聚合物(A))為，具有由下述式[1A](亦稱為特定結構(1A))，及[1B](亦稱為特定結構(1B))所成之群所選出之至少1種之結構之聚醯亞胺前驅物及該聚醯亞胺前驅物經醯亞胺化所得之聚醯亞胺所成之群所選出之至少1種的聚合物。 The component (A) of the present invention (hereinafter also referred to as a specific polymer (A)) has the following formula [1A] (also referred to as a specific structure (1A)), and [1B] (also referred to as a specific The polyimine precursor of the structure selected from the group consisting of the structure (1B)) and the polyimine imide obtained by the ruthenium imidization of the polyamidene precursor are selected At least one polymer.

式[1A]中，XA為經由熱而被取代為氫原子之基。該基係指，鍵結於氮原子，經由熱而解離而被取代為氫原子，形成胺基之保護基之意。該保護基經由熱而解離，被取代為氫原子之溫度，為製作液晶配向膜時的燒結溫度，較佳為150~300℃、更佳為200~270。該保護基，只要經由熱而解離，被取代為氫原子者時，並未有特別之限 定，具體而言，可列舉如，由下述式[a-1]~式[a-6]所成之群所選出之至少1種，其中，又以具有式[a-1]或[a-6]所表示之結構的保護基為佳。 In the formula [1A], X A is a group substituted with a hydrogen atom via heat. This group means a bond which is bonded to a nitrogen atom, is dissociated by heat, and is substituted with a hydrogen atom to form a protective group of an amine group. The protective group is dissociated by heat and is substituted with a hydrogen atom. The sintering temperature at the time of producing the liquid crystal alignment film is preferably from 150 to 300 ° C, more preferably from 200 to 270. The protective group is not particularly limited as long as it is dissociated by heat and is substituted with a hydrogen atom. Specifically, it is exemplified by the following formula [a-1] to formula [a-6]. At least one selected from the group is preferably a protecting group having a structure represented by the formula [a-1] or [a-6].

(式[a-2]中，R1表示碳數1~5之烷基。) (In the formula [a-2], R 1 represents an alkyl group having 1 to 5 carbon atoms.)

式[1A]以下述式[1a]及式[1b]所表示之結構為佳。 The formula [1A] is preferably a structure represented by the following formula [1a] and formula [1b].

式[1a]中，Xa表示氫原子或碳數1~20之有機基。其中，又以氫原子或碳數1~10之有機基為佳。式[1a]中之Xb，及式[1b]中之Xc為經由熱而被取代為氫原子之基，為羧基之保護基。Xb、Xc，與上述XA為相同內容，較佳之例示亦為相同。 In the formula [1a], X a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. Among them, a hydrogen atom or an organic group having 1 to 10 carbon atoms is preferred. X b in the formula [1a] and X c in the formula [1b] are a group substituted with a hydrogen atom via heat, and are a protecting group of a carboxyl group. X b and X c are the same as X A above, and preferred examples are also the same.

式[1a]中，m表示1或2之整數，m為2之情形中，Xa不具有取代基。m以1為佳。 In the formula [1a], m represents an integer of 1 or 2, and in the case where m is 2, X a does not have a substituent. m is preferably 1.

具有式[1a]及/或[1b]之結構的具體例，可列舉如，下述式[XA-1]~式[XA-12]之結構等。 Specific examples of the structure of the formula [1a] and/or [1b] include the structures of the following formula [XA-1] to the formula [XA-12].

(式[XA-1]~式[XA-6]中，A1~A6各自獨立表示由前述式[a-1]~式[a-6]所成之群所選出之至少1種。式[XA-1]中，n1表示0~10之整數，式[XA-2]~式[XA-6]中，n2~n6表示1~10之整數)。 (In the formula [XA-1] to the formula [XA-6], each of A 1 to A 6 independently represents at least one selected from the group consisting of the above formulas [a-1] to [a-6]. In the formula [XA-1], n1 represents an integer of 0 to 10, and in the formula [XA-2]~form [XA-6], n2 to n6 represent an integer of 1 to 10).

(式[XA-7]~式[XA-12]中，A7~A18各自獨立表示由前述式[a-1]~式[a-6]所成之群所選出之至少1種。式[XA-7]中，n7表示0~10之整數，式[XA-8]~式[XA-12]中，n8~n12表示1~10之整數)。 (In the formula [XA-7] to the formula [XA-12], A 7 to A 18 each independently represent at least one selected from the group consisting of the above formulas [a-1] to [a-6]. In the formula [XA-7], n7 represents an integer of 0 to 10, and in the formula [XA-8]~form [XA-12], n8 to n12 represent an integer of 1 to 10).

式[1B]中，XB表示單鍵或碳數1~40之有機基。碳數1~40之有機基，具體而言，可列舉如，可含有醚鍵結(-O-)、醯胺鍵結(-CONH-或NHCO-)、酯鍵結(-COO-或OCO-)、硫醚鍵結(-S-)或硫酯鍵結(-S(=O)2- )之伸烷基、伸芳基或該些之組合等。此時，式[1B]中之酯基(-COO-)所鍵結之原子為碳原子。 In the formula [1B], X B represents a single bond or an organic group having 1 to 40 carbon atoms. The organic group having 1 to 40 carbon atoms, specifically, for example, may contain an ether bond (-O-), a guanamine bond (-CONH- or NHCO-), an ester bond (-COO- or OCO). -), a thioether linkage (-S-) or a thioester linkage (-S(=O) 2 - ) alkylene group, an extended aryl group or a combination thereof. At this time, the atom to which the ester group (-COO-) in the formula [1B] is bonded is a carbon atom.

式[1B]中，XC為經由熱而被取代為氫原子之基，為羧基之保護基。Xb、Xc與上述XA為相同內容，較佳之例示亦為相同。 In the formula [1B], X C is a group substituted with a hydrogen atom via heat, and is a protective group of a carboxyl group. X b and X c are the same as X A above, and preferred examples are also the same.

前述式[1B]，以下述式[1c]所表示之結構為佳。 The above formula [1B] is preferably a structure represented by the following formula [1c].

式[1c]中，Xd表示單鍵或碳數1~20之有機基，此時，Xd，為單鍵之情形，則不具取代基Xe。其中，又以單鍵或碳數1~10之有機基為佳。Xe，於Xd不為單鍵之情形，表示氫原子或碳數1~20之有機基。其中，又以氫原子或碳數1~10之有機基為佳。Xf為經由熱而被取代為氫原子之基，為羧基之保護基。Xf與上述XA為相同內容，較佳之例示亦為相同。n表示1~4之整數。其中，又以1或2為佳。 In the formula [1c], X d represents a single bond or an organic group having 1 to 20 carbon atoms. In this case, when X d is a single bond, the substituent X e is not contained. Among them, a single bond or an organic group having 1 to 10 carbon atoms is preferred. X e , in the case where X d is not a single bond, represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. Among them, a hydrogen atom or an organic group having 1 to 10 carbon atoms is preferred. X f is a group substituted with a hydrogen atom via heat and is a protective group of a carboxyl group. X f is the same as X A above, and the preferred examples are also the same. n represents an integer from 1 to 4. Among them, 1 or 2 is preferred.

式[1c]之結構之具體例，可列舉如，下述式[XC-1]~[XC-12]之結構等。 Specific examples of the structure of the formula [1c] include the structures of the following formulas [XC-1] to [XC-12].

(式[XC-1]~式[XC-6]中，B1~B6各自獨立表示由前述式[a-1]~式[a-6]所成之群所選出之至少1種。式[XC-1]中，n1表示0~10之整數，式[XC-2]~式[XC-6]中，n2~n6表示1~10之整數)。 (In the formula [XC-1] to the formula [XC-6], B 1 to B 6 each independently represent at least one selected from the group consisting of the above formulas [a-1] to [a-6]. In the formula [XC-1], n1 represents an integer of 0 to 10, and in the formula [XC-2]~form [XC-6], n2 to n6 represent an integer of 1 to 10).

(式[XC-7]~式[XC-12]中，B7~B18各自獨立表示由前述式[a-1]~式[a-6]所成之群所選出之至少1種。式[XC-7]中，n7表示0~10之整數，式[XC-8]~式[XC-12]中，n8~n12表示1~10之整數)。 (In the formula [XC-7] to the formula [XC-12], B 7 to B 18 each independently represent at least one selected from the group consisting of the above formulas [a-1] to [a-6]. In the formula [XC-7], n7 represents an integer of 0 to 10, and in the formula [XC-8]~form [XC-12], n8 to n12 represent an integer of 1 to 10).

<特定聚合物(A)> <Specific polymer (A)>

本發明之特定聚合物(A)為，由聚醯亞胺前驅物及該聚醯亞胺前驅物經醯亞胺化而得之聚醯亞胺(亦統稱為聚醯亞胺系聚合物)所成之群所選出之至少1種的聚合物。其中，本發明之聚醯亞胺系聚合物，又以二胺成份與四羧酸成份反應所得之聚醯亞胺前驅物或該聚醯亞胺前驅物經醯亞胺化所得之聚醯亞胺為佳。 The specific polymer (A) of the present invention is a polyimine (also collectively referred to as a polyamidene-based polymer) obtained by imidization of a polyimide precursor and the polyimide precursor. At least one polymer selected from the group formed. Wherein the polyamidene-based polymer of the present invention is obtained by reacting a polyimine precursor obtained by reacting a diamine component with a tetracarboxylic acid component or a polyazide precursor obtained by ruthenium imidization of the polyimide precursor Amine is preferred.

聚醯亞胺前驅物係為下述式[A]所表示之結構。 The polyimine precursor is a structure represented by the following formula [A].

(式[A]中，R1為4價之有機基，R2為2價之有機基，A1及A2各自獨立表示氫原子或碳數1~5之烷基。A3及A4各自獨立表示氫原子、碳數1~10之烷基、碳數1~10之烯基，或碳數1~10之炔基，該些之基可具有取代基。n表示正整數)。 (In the formula [A], R 1 is a tetravalent organic group, R 2 is a divalent organic group, and A 1 and A 2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A 3 and A 4 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, and these groups may have a substituent. n represents a positive integer).

前述二胺成份，可列舉如，分子內具有2個一級或二級胺基之二胺等。 The diamine component may, for example, be a diamine having two primary or secondary amine groups in the molecule.

前述四羧酸成份，可列舉如，四羧酸、四羧酸二酐、四羧酸二鹵化物、四羧酸二烷酯，或四羧酸二烷酯二鹵化物等。 Examples of the tetracarboxylic acid component include a tetracarboxylic acid, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide, a dicarboxylic acid dialkyl ester, or a tetracarboxylic acid dialkyl ester dihalide.

欲製得式[A]中之A1及A2為氫原子之聚醯胺酸，可前述分子內具有2個一級或二級胺基之二胺，與四羧酸化合物或四羧酸二酐進行反應而可製得。 To obtain a polyamic acid in which A 1 and A 2 in the formula [A] are hydrogen atoms, a diamine having two primary or secondary amine groups in the molecule, and a tetracarboxylic acid compound or a tetracarboxylic acid An anhydride can be obtained by reacting.

欲製得式[A]中之A1及A2為碳數1~5之烷基的聚醯胺酸烷酯，可將前述二胺，與四羧酸二鹵化物、四羧酸二烷酯或四羧酸二烷酯二鹵化物進行反應而可製得。又，亦可於前述方法所得之聚醯胺酸中，導入式[A]所表示之A1及A2之碳數1~5之烷基亦可。 To obtain an alkyl amide of the formula [A] wherein A 1 and A 2 are alkyl groups having 1 to 5 carbon atoms, the diamine, the tetracarboxylic acid dihalide, and the tetracarboxylic acid dioxane may be used. The ester or tetracarboxylic acid dialkyl ester dihalide can be obtained by reacting. Further, an alkyl group having 1 to 5 carbon atoms of A 1 and A 2 represented by the formula [A] may be introduced into the polyamic acid obtained by the above method.

本發明之特定聚合物(A)為具有由特定結構(1A)及特定結構(1B)所成之群所選出之至少1種的聚合物。 The specific polymer (A) of the present invention is a polymer having at least one selected from the group consisting of the specific structure (1A) and the specific structure (1B).

將本發明之特定結構(1A)或特定結構(1B)導入特定聚合物(A)中之方法，並未有特別之限定，又以使用具有特定結構(1A)或特定結構(1B)的二胺作為二胺成份使用者為佳。特佳為使用具有前述式[1a]、式[1b]或式[1c]所表示之結構的二胺。 The method of introducing the specific structure (1A) or the specific structure (1B) of the present invention into the specific polymer (A) is not particularly limited, and a second one having a specific structure (1A) or a specific structure (1B) is used. The amine is preferred as the user of the diamine component. It is particularly preferable to use a diamine having a structure represented by the above formula [1a], formula [1b] or formula [1c].

具體而言，可列舉如，以使用下述式[1-1]所表示之二胺(亦稱為特定二胺(1))為佳。 Specifically, for example, a diamine (also referred to as a specific diamine (1)) represented by the following formula [1-1] is preferably used.

式[1-1]中，A1及A2各自獨立表示氫原子、碳數1~10之烷基、碳數1~10之烯基，或碳數1~10之炔基，該些之基可具有取代基。 In the formula [1-1], A 1 and A 2 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms. The group may have a substituent.

烷基之具體例，可列舉如，甲基、乙基、丙基、丁基、t-丁基、己基、辛基、癸基、環戊基、環己基等。 Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, and a cyclohexyl group.

烯基例如，使上述之烷基所存的1個以上之CH2-CH2結構取代為CH=CH結構者。具體而言，可列舉如，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。 The alkenyl group is, for example, a structure in which one or more CH 2 -CH 2 structures existing in the above alkyl group are substituted with a CH=CH structure. Specific examples thereof include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, and a 2-hexenyl group. And cyclopropenyl, cyclopentenyl, cyclohexenyl and the like.

炔基例如，使上述之烷基所存的1個以上之CH2-CH2結構取代為C≡C結構者。具體而言，可列舉如，乙炔基、1-丙炔基、2-丙炔基等。 The alkynyl group is, for example, a structure in which one or more CH 2 -CH 2 structures existing in the above alkyl group are substituted with a C≡C structure. Specific examples thereof include an ethynyl group, a 1-propynyl group, and a 2-propynyl group.

上述之烷基、烯基，及炔基，其全體為碳數1~10者時亦可具有取代基，此外，取代基亦可形成環結 構。又，取代基形成環結構之意，係指取代基相互間或取代基與母骨架之一部份鍵結形成環結構之意。 The above alkyl group, alkenyl group, and alkynyl group may have a substituent when the total number of carbon atoms is 1 to 10, and the substituent may also form a ring knot. Structure. Further, the meaning of the substituent forming a ring structure means that the substituents are bonded to each other or a part of the substituent is bonded to a part of the parent skeleton to form a ring structure.

取代基之例，可列舉如，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。 Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate group, and the like. Amidino, alkyl, alkenyl, alkynyl and the like.

作為取代基之鹵素基，可列舉如，氟原子、氯原子、溴原子，或碘原子等。 The halogen group as a substituent may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

作為取代基之芳基，可列舉如，苯基。該芳基上可再被前述其他之取代基所再取代。 The aryl group as a substituent may, for example, be a phenyl group. The aryl group may be further substituted with the other substituents described above.

作為取代基之有機氧基，可列舉如，如-O-R所表示之結構等例示。R，可例如前述之烷基、烯基、炔基、芳基等例示。該些之R中，前述之取代基可再被取代。烷氧基之具體例，可列舉如，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。 Examples of the organooxy group as the substituent include, for example, a structure represented by -O-R. R may, for example, be exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. In the above R, the aforementioned substituent may be further substituted. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.

作為取代基之有機硫基，可列舉如，如-S-R所表示之結構等例示。R，可例如前述之烷基、烯基、炔基、芳基等例示。該些之R中，前述之取代基可再被取代。烷硫基之具體例，可列舉如，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。 Examples of the organic sulfur group as a substituent include, for example, a structure represented by -S-R. R may, for example, be exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. In the above R, the aforementioned substituent may be further substituted. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.

作為取代基之有機矽烷基，可列舉如，如-Si-(R)3所表示之結構等例示。Si上的3個R可為相同或相異皆可，其可例如前述烷基、烯基、炔基、芳基等例示。該些之R中，前述之取代基可再被取代。烷基矽烷基之具體例，可列舉如，三甲基矽烷基、三乙基矽烷基、三丙基矽 烷基、三丁基矽烷基、三戊基矽烷基、三己基矽烷基、戊基二甲基矽烷基、己基二甲基矽烷基等。 The organic decyl group as a substituent may, for example, be exemplified by a structure represented by -Si-(R) 3 or the like. The three R groups on Si may be the same or different, and may be exemplified, for example, by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group or the like. In the above R, the aforementioned substituent may be further substituted. Specific examples of the alkylalkylalkyl group include, for example, trimethyldecylalkyl group, triethylsulfonylalkyl group, tripropyldecylalkyl group, tributylsulfonylalkyl group, tripentyldecylalkyl group, trihexyldecylalkyl group, and pentyl group Methyl decyl group, hexyl dimethyl decyl group, and the like.

作為取代基之醯基，可列舉如，如-C(O)-R所表示之結構等例示。R，可例如前述烷基、烯基、芳基等例示。該些之R中，前述之取代基可再被取代。醯基的具體例示，可列舉如，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。 Examples of the thiol group as the substituent include, for example, a structure represented by -C(O)-R. R, for example, the aforementioned alkyl group, alkenyl group, aryl group or the like can be exemplified. In the above R, the aforementioned substituent may be further substituted. Specific examples of the mercapto group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a benzamidine group, and the like.

作為取代基之酯基，可列舉如，如-C(O)O-R，或-OC(O)-R所表示之結構等例示。R，可例如前述之烷基、烯基、炔基、芳基等例示。該些之R中，前述之取代基可再被取代。 The ester group as a substituent may, for example, be exemplified by a structure represented by -C(O)O-R or -OC(O)-R. R may, for example, be exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. In the above R, the aforementioned substituent may be further substituted.

作為取代基之硫酯基，可列舉如，如-C(S)O-R，或-OC(S)-R所表示之結構等例示。R，可例如前述之烷基、烯基、炔基、芳基等例示。該些之R中，前述之取代基可再被取代。 The thioester group as a substituent may, for example, be exemplified by a structure represented by -C(S)O-R or -OC(S)-R. R may, for example, be exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. In the above R, the aforementioned substituent may be further substituted.

作為取代基之磷酸酯基，可列舉如，如-OP(O)-(OR)2所表示之結構等例示。2個之R可為相同或相異皆可，其可例如前述烷基、烯基、炔基、芳基等例示。該些之R中，前述之取代基可再被取代。 The phosphate group as a substituent may, for example, be exemplified by a structure represented by -OP(O)-(OR) 2 or the like. The two R's may be the same or different, and may, for example, be exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. In the above R, the aforementioned substituent may be further substituted.

作為取代基之醯胺基，可列舉如，如-C(O)NH2、-C(O)NHR、-NHC(O)R、-C(O)N(R)2，或-NRC(O)R所表示之結構等例示。該些之R可為相同或相異皆可，其可例如前述烷基、烯基、炔基、芳基等例示。該些之R中，前述之取代基可再被取代。 Examples of the sulfhydryl group as a substituent include, for example, -C(O)NH 2 , -C(O)NHR, -NHC(O)R, -C(O)N(R) 2 , or -NRC ( O) The structure and the like represented by R are exemplified. These R may be the same or different, and may, for example, be exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. In the above R, the aforementioned substituent may be further substituted.

作為取代基之芳基，可列舉如，與前述之芳基為相同之內容等。該芳基中，前述其他之取代基可再被取代。 The aryl group as a substituent may, for example, be the same as the above-mentioned aryl group. In the aryl group, the other substituents described above may be further substituted.

作為取代基之烷基，可列舉如，與前述之烷基為相同之內容等。該烷基中，前述其他之取代基可再被取代。 The alkyl group as a substituent may, for example, be the same as the above-mentioned alkyl group. In the alkyl group, the other substituents described above may be further substituted.

作為取代基之烯基，可列舉如，與前述之烯基為相同之內容等。該烯基中，前述其他之取代基可再被取代。 The alkenyl group as a substituent may, for example, be the same as the above-mentioned alkenyl group. In the alkenyl group, the other substituents described above may be further substituted.

作為取代基之炔基，可列舉如，與前述之炔基為相同之內容等。該炔基中，前述其他之取代基可再被取代。 The alkynyl group as a substituent may, for example, be the same as the alkynyl group described above. In the alkynyl group, the other substituents described above may be further substituted.

一般而言，導入高體積密度之結構時，因會有降低胺基之反應性或液晶配向性之可能性，故A1及A2以氫原子，或可具有取代基之碳數1~5之烷基為較佳，以氫原子、甲基或乙基為特佳。 In general, when a structure having a high bulk density is introduced, A 1 and A 2 may have a hydrogen atom or a carbon number of 1 to 5 which may have a substituent because of a possibility of lowering the reactivity of the amine group or the liquid crystal alignment property. The alkyl group is preferably a hydrogen atom, a methyl group or an ethyl group.

式[1-1]中，XD表示具有由前述式[1a]、式[1b]及式[1c]所表示之結構所成之群所選出之至少1種的碳數5~50之有機基。 In the formula [1-1], X D represents at least one organic compound having 5 to 50 carbon atoms selected from the group consisting of the structures represented by the above formulas [1a], [1b], and [1c]. base.

更具體而言，可列舉如，以下述式[1a-1]~式[1c-1]所表示之二胺為佳。 More specifically, for example, a diamine represented by the following formula [1a-1] to formula [1c-1] is preferred.

式[1a-1]中，X1表示由單鍵、碳數1~10之伸烷基、-O-、-N(R1)-、-CON(R2)-、-N(R3)CO-、-CH2O-、-COO-及-OCO-所選出之至少1種。但，R1、R2及R3各自獨立表示氫原子或碳數1~3之烷基。其中，又以單鍵、-O-、-CONH-、-NHCO-、-COO-或-OCO-為佳。 In the formula [1a-1], X 1 represents a single bond, an alkyl group having 1 to 10 carbon atoms, -O-, -N(R 1 )-, -CON(R 2 )-, -N(R 3 At least one selected from the group consisting of CO-, -CH 2 O-, -COO-, and -OCO-. However, R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among them, a single bond, -O-, -CONH-, -NHCO-, -COO- or -OCO- is preferred.

式[1a-1]中，X2表示單鍵或碳數1~10之伸烷基。其中，又以單鍵或碳數1~5之伸烷基為佳。 In the formula [1a-1], X 2 represents a single bond or an alkylene group having 1 to 10 carbon atoms. Among them, a single bond or an alkyl group having 1 to 5 carbon atoms is preferred.

式[1a-1]中，Xa表示氫原子或碳數1~20之有機基，更佳為氫原子或碳數1~10之有機基。碳數1~10之有機基，以-(CH2)n-COO-tBu(n=1~5之整數，tBu表示tert-丁基)為佳。Xb與前述式[1A]中之XA為相同內容，較佳之例示亦為相同。 In the formula [1a-1], X a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an organic group having 1 to 10 carbon atoms. The organic group having 1 to 10 carbon atoms is preferably -(CH 2 ) n -COO-tBu (an integer of n = 1 to 5, and tt represents a tert-butyl group). X b is the same as X A in the above formula [1A], and preferred examples are also the same.

式[1a-1]中，m表示1或2之整數，m為2之情形中，Xa不具有取代基。p表示1~4之整數。其中，就原料取得性或合成之容易性等觀點，以1~3為佳，更佳為 1~2。q表示1~4之整數。其中，就原料取得性或合成之容易性等觀點，以1~3為佳，更佳為1~2。 In the formula [1a-1], m represents an integer of 1 or 2, and in the case where m is 2, X a does not have a substituent. p represents an integer from 1 to 4. Among them, from the viewpoints of availability of raw materials or easiness of synthesis, it is preferably 1 to 3, more preferably 1 to 2. q represents an integer from 1 to 4. Among them, from the viewpoints of availability of raw materials or easiness of synthesis, it is preferably 1 to 3, more preferably 1 to 2.

式[1b-1]中，X3及X7與前述式[1a-1]中之X1為相同內容，較佳之例示亦為相同。X4、X5及X6與前述式[1a-1]中之X2為相同內容，較佳之例示亦為相同。Xc與前述式[1A]中之XA為相同內容，較佳之例示亦為相同。r表示1~4之整數。其中，就原料取得性或合成之容易性等觀點，以1~3為佳。更佳者為，1~2。 In the formula [1b-1], X 3 and X 7 are the same as X 1 in the above formula [1a-1], and preferred examples are also the same. X 4 , X 5 and X 6 are the same as X 2 in the above formula [1a-1], and preferred examples are also the same. X c is the same as X A in the above formula [1A], and preferred examples are also the same. r represents an integer from 1 to 4. Among them, from the viewpoints of availability of raw materials or easiness of synthesis, it is preferably 1 to 3. The better is, 1~2.

式[1c-1]中，X8與前述式[1a-1]中之X1為相同之定義，較佳之例示亦為相同之意義。X9與前述式[1a-1]中之X2為相同內容，較佳之例示亦為相同。Xd表示單鍵或碳數1~20之有機基。其中，又以單鍵或碳數1~10之有機基為佳。更佳為單鍵或碳原子(>CH-)。Xe表示氫原子或碳數1~20之有機基。Xd為單鍵之情形中，則不具有取代基Xe。其中，又以氫原子或-NH-COO-tBu(tBu表示tert-丁基)為佳。Xf與前述式[1a]中之Xb為相同內容，較佳之例示亦為相同。 In the formula [1c-1], X 8 is the same as X 1 in the above formula [1a-1], and preferred examples are also of the same meaning. X 9 is the same as X 2 in the above formula [1a-1], and preferred examples are also the same. X d represents a single bond or an organic group having 1 to 20 carbon atoms. Among them, a single bond or an organic group having 1 to 10 carbon atoms is preferred. More preferably, it is a single bond or a carbon atom (>CH-). X e represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. In the case where X d is a single bond, there is no substituent X e . Among them, a hydrogen atom or -NH-COO-tBu (tBu represents tert-butyl) is preferred. X f is the same as X b in the above formula [1a], and preferred examples are also the same.

n、s及t表示1~4之整數。其中，就原料取得性或合成之容易性等觀點，以分別為1~3為佳，更佳者為，1~2。 n, s, and t represent integers from 1 to 4. Among them, from the viewpoints of availability of raw materials or easiness of synthesis, it is preferably 1 to 3, and more preferably 1 to 2.

式[1a-1]~式[1c-1]中，A1~A6包含較佳之例示，為與式[1-1]之A1及A2為相同之定義。 In the formula [1a-1] to the formula [1c-1], A 1 to A 6 are preferably exemplified, and are the same definitions as A 1 and A 2 of the formula [1-1].

此外，具體的二胺，可列舉如，下述式[1d-1]~式[1d-9]之二胺。 Further, specific examples of the diamine include a diamine of the following formula [1d-1] to formula [1d-9].

式[1d-1]~[1d-5]中，R1~R7各自獨立表示由前述式[a-1]~式[a-6]所成之群所選出之至少1種。A1~A10包含較佳之例示，為與式[1-1]之A1及A2為相同之定義。 In the formulae [1d-1] to [1d-5], R 1 to R 7 each independently represent at least one selected from the group consisting of the above formulas [a-1] to [a-6]. A 1 to A 10 contain a preferred example and are the same definitions as A 1 and A 2 of the formula [1-1].

式[1d-6]~式[1d-9]中，R8~R14各自獨立表示由前述式[a-1]~式[a-6]所成之群所選出之至少1種。A11~A18包含較佳之例示，為與式[1-1]之A1及A2為相同之定義。 In the formula [1d-6] to the formula [1d-9], R 8 to R 14 each independently represent at least one selected from the group consisting of the above formulas [a-1] to [a-6]. A 11 to A 18 contain preferred examples, and are the same definitions as A 1 and A 2 of the formula [1-1].

本發明之特定二胺(1)，以使用由前述式[1d-1]~式[1d-5]所表示之二胺所成之群所選出之至少1 種為佳。 The specific diamine (1) of the present invention is at least 1 selected from the group consisting of the diamine represented by the above formula [1d-1] to the formula [1d-5]. Kind is better.

特定聚合物(A)中之特定二胺(1)，以於全部之二胺成份100莫耳%中，為5~40莫耳%為佳。其中，又以5~30莫耳%為佳。較佳為，5~20莫耳%。 The specific diamine (1) in the specific polymer (A) is preferably from 5 to 40 mol%, based on 100 mol% of the total diamine component. Among them, 5 to 30 mol% is preferred. Preferably, it is 5 to 20 mol%.

特定二胺(1)，可配合特定聚合物(A)對於溶劑之溶解性，或液晶配向劑之塗佈性、作為液晶配向膜之情形中的液晶配向性、電壓保持率、蓄積電荷等之特性等，可使用1種類或將2種類以上混合使用亦可。 The specific diamine (1) can be blended with a solvent of a specific polymer (A), a coating property of a liquid crystal alignment agent, a liquid crystal alignment property as a liquid crystal alignment film, a voltage retention ratio, an accumulated charge, and the like. For the characteristics, etc., one type or two types or more may be used in combination.

製造特定聚合物(A)時之二胺成份中，特定二胺(1)以使用下述式[3-1]所表示之其他之二胺(亦稱為特定第2之二胺)為佳。 Among the diamine components in the production of the specific polymer (A), it is preferred that the specific diamine (1) is other diamine (also referred to as a specific second diamine) represented by the following formula [3-1]. .

式[3-1]中，XE為下述式[3a-1]~式[3a-9]所示結構所選出之至少1個。 In the formula [3-1], X E is at least one selected from the structures represented by the following formula [3a-1] to the formula [3a-9].

(式[3a-9]中，n表示1~5之整數)。 (in the formula [3a-9], n represents an integer of 1 to 5).

式[3-1]中，A1及A2各自獨立表示氫原子或碳數1~5之烷基。 In the formula [3-1], A 1 and A 2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

特定第2之二胺，以式[3a-1]~式[3a-4]、式[3a-6]、式[3a-8]或式[3a-9]之二胺為佳。較佳為，式[3a-1]~式[3a-3]、式[3a-8]或式[3a-9]。特佳為式[3a-1]、式[3a-2]或式[3a-9]。 The specific second bisamine is preferably a diamine of the formula [3a-1] to the formula [3a-4], the formula [3a-6], the formula [3a-8] or the formula [3a-9]. Preferably, the formula [3a-1] to the formula [3a-3], the formula [3a-8] or the formula [3a-9]. Particularly preferred is the formula [3a-1], the formula [3a-2] or the formula [3a-9].

特定聚合物(A)中之特定第2之二胺，於全部二胺成份100莫耳%中，以50~95莫耳%為佳，更佳為60~95莫耳%，特佳為80~95莫耳%。 The specific second diamine in the specific polymer (A) is preferably from 50 to 95 mol%, more preferably from 60 to 95 mol%, more preferably from 80 to 95 mol%, based on 100 mol% of the total diamine component. ~95 moles %.

特定第2之二胺，可配合特定聚合物(A)對於溶劑之溶解性，或液晶配向劑之塗佈性、作為液晶配向膜之情形中的液晶配向性、電壓保持率、蓄積電荷等之特性等，使用1種類或將2種類以上混合使用。 The specific second bisamine can be blended with a solvent of a specific polymer (A), a coating property of a liquid crystal alignment agent, a liquid crystal alignment property as a liquid crystal alignment film, a voltage retention ratio, an accumulated charge, and the like. For the characteristics, etc., use 1 type or mix 2 types or more.

特定聚合物(A)及特定聚合物(B)之二胺成份，於無損本發明效果之範圍內，與特定二胺(1)、特定二胺(2)及特定第2之二胺同時，可使用其他之二胺(亦稱為其他二胺)。 The diamine component of the specific polymer (A) and the specific polymer (B), together with the specific diamine (1), the specific diamine (2) and the specific second diamine, is within the range which does not impair the effects of the present invention. Other diamines (also known as other diamines) can be used.

其他二胺，可列舉如，2,4-二甲基-m-伸苯基二胺、2,6-二胺基甲苯、m-伸苯基二胺、p-伸苯基二胺、4,4’-二胺基聯苯基、3,3’-二甲基-4,4’-二胺基聯苯基、3,3’-二甲氧基-4,4’-二胺基聯苯基、3,3’-二羥基-4,4’-二胺基聯苯基、3,3’-二羧基-4,4’-二胺基聯苯基、3,3’-二氟-4,4’-聯苯基、3,3’-三氟甲基-4,4’-二胺基聯苯基、3,4’-二胺基聯苯基、3,3’-二胺基聯苯基、2,2’-二胺基聯苯基、2,3’-二胺基 聯苯基、4,4’-二胺基二苯基甲烷、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、2,2’-二胺基二苯基甲烷、2,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、2,2’-二胺基二苯基醚、2,3’-二胺基二苯基醚、4,4’-磺醯基二苯胺、3,3’-磺醯基二苯胺、雙(4-胺基苯基)矽烷、雙(3-胺基苯基)矽烷、二甲基-雙(4-胺基苯基)矽烷、二甲基-雙(3-胺基苯基)矽烷、4,4’-硫代二苯胺、3,3’-硫代二苯胺、4,4’-二胺基二苯基胺、3,3’-二胺基二苯基胺、3,4’-二胺基二苯基胺、2,2’-二胺基二苯基胺、2,3’-二胺基二苯基胺、N-甲基(4,4’-二胺基二苯基)胺、N-甲基(3,3’-二胺基二苯基)胺、N-甲基(3,4’-二胺基二苯基)胺、N-甲基(2,2’-二胺基二苯基)胺、N-甲基(2,3’-二胺基二苯基)胺、4,4’-二胺基二苯甲酮、3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、1,4-二胺基萘、2,2’-二胺基二苯甲酮、2,3’-二胺基二苯甲酮、1,5-二胺基萘、1,6-二胺基萘、1,7-二胺基萘、1,8-二胺基萘、2,5-二胺基萘、2,6二胺基萘、2,7-二胺基萘、2,8-二胺基萘、1,2-雙(4-胺基苯基)乙烷、1,2-雙(3-胺基苯基)乙烷、1,3-雙(4-胺基苯基)丙烷、1,3-雙(3-胺基苯基)丙烷、1,4-雙(4胺基苯基)丁烷、1,4-雙(3-胺基苯基)丁烷、雙(3,5-二乙基-4-胺基苯基)甲烷、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、1,4-雙(4-胺基苄基)苯、1,3-雙(4-胺基苯氧基)苯、 4,4’-[1,4-伸苯基雙(伸甲基)]二苯胺、4,4’-[1,3-伸苯基雙(伸甲基)]二苯胺、3,4’-[1,4-伸苯基雙(伸甲基)]二苯胺、3,4’-[1,3-伸苯基雙(伸甲基)]二苯胺、3,3’-[1,4-伸苯基雙(伸甲基)]二苯胺、3,3’-[1,3-伸苯基雙(伸甲基)]二苯胺、1,4-伸苯基雙[(4-胺基苯基)甲酮]、1,4-伸苯基雙[(3-胺基苯基)甲酮]、1,3-伸苯基雙[(4-胺基苯基)甲酮]、1,3-伸苯基雙[(3-胺基苯基)甲酮]、1,4-伸苯基雙(4-胺基苯甲酸酯)、1,4-伸苯基雙(3-胺基苯甲酸酯)、1,3-伸苯基雙(4-胺基苯甲酸酯)、1,3-伸苯基雙(3-胺基苯甲酸酯)、雙(4-胺基苯基)對苯二甲酸酯、雙(3-胺基苯基)對苯二甲酸酯、雙(4-胺基苯基)間苯二甲酸酯、雙(3-胺基苯基)間苯二甲酸酯、N,N’-(1,4-伸苯基)雙(4-胺基苯甲醯胺)、N,N’-(1,3-伸苯基)雙(4-胺基苯甲醯胺)、N,N’-(1,4-伸苯基)雙(3-胺基苯甲醯胺)、N,N’-(1,3-伸苯基)雙(3-胺基苯甲醯胺)、N,N’-雙(4-胺基苯基)對苯二甲醯胺、N,N’-雙(3-胺基苯基)對苯二甲醯胺、N,N’-雙(4-胺基苯基)異苯二甲醯胺、N,N’-雙(3-胺基苯基)異苯二甲醯胺、9,10-雙(4-胺基苯基)蒽、4,4’-雙(4-胺基苯氧基)二苯基碸、2,2’-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2’-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2’-雙(4-胺基苯基)六氟丙烷、2,2’-雙(3-胺基苯基)六氟丙烷、2,2’-雙(3-胺基-4-甲基苯基)六氟丙烷、2,2’-雙(4-胺基苯基)丙烷、2,2’-雙(3-胺基苯基)丙烷、2,2’-雙(3-胺基-4-甲基 苯基)丙烷、1,3-雙(4-胺基苯氧基)丙烷、1,3-雙(3-胺基苯氧基)丙烷、1,4-雙(4-胺基苯氧基)丁烷、1,4-雙(3-胺基苯氧基)丁烷、1,5-雙(4-胺基苯氧基)戊烷、1,5-雙(3-胺基苯氧基)戊烷、1,6-雙(4-胺基苯氧基)己烷、1,6-雙(3-胺基苯氧基)己烷、1,7-雙(4-胺基苯氧基)庚烷、1,7-(3-胺基苯氧基)庚烷、1,8-雙(4-胺基苯氧基)辛烷、1,8-雙(3-胺基苯氧基)辛烷、1,9-雙(4-胺基苯氧基)壬烷、1,9-雙(3-胺基苯氧基)壬烷、1,10-(4-胺基苯氧基)癸烷、1,10-(3-胺基苯氧基)癸烷、1,11-(4-胺基苯氧基)十一烷、1,11-(3-胺基苯氧基)十一烷、1,12-(4-胺基苯氧基)十二烷、1,12-(3-胺基苯氧基)十二烷、雙(4-胺基環己基)甲烷、雙(4-胺基-3-甲基環己基)甲烷、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷、1,12-二胺基十二烷，或該些之胺基為二級胺基之二胺等。其他二胺可使用1種類或將2種類以上混合使用。 Other diamines may, for example, be 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 4 , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diamino Biphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-di Fluorin-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'- Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diamino Biphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diamine Diphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'- Diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'- Sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis (3) -aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiyl Phenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4, 4'-Diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone , 3,3'-diaminobenzophenone, 3,4 '-Diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-di Amino naphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2, 7-Diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1, 3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3) -aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-double ( 4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-amino group Benzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methyl)diphenylamine, 4,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,4' -[1,4-phenylenebis(methyl)diphenylamine, 3,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,3'-[1, 4-phenylene bis(methyl)diphenylamine, 3,3'-[1,3-phenylenebis(methyl)diphenylamine, 1,4-phenylene bis[(4- Aminophenyl)methanone], 1,4-phenylphenylbis[(3-aminophenyl)methanone], 1,3-phenylphenylbis[(4-aminophenyl)methanone] , 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylene bis ( 3-amino benzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoate), double 4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3- Aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene) Bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3- Phenyl) bis(3-aminobenzamide), N,N'-bis(4-amine Phenylphenyl) p-xylguanamine, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)isophthalate Indoleamine, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-amino group Phenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-double ( 3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2, 2'-bis(3-amino-4-methyl Phenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy) Butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxyl) Pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminobenzene) Oxy) heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminobenzene Oxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminobenzene Oxy) decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxyl) Ethyl undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane , bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6- Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11- Diaminoundecane, 1,12-diamine Dodecane, or a group of the plurality of secondary amino groups of the diamine. Other diamines may be used in combination of one type or two or more types.

製造特定聚合物(A)所使用之四羧酸成份，以下述式[4]所表示之四羧酸二酐為佳。此時，不僅式[4]所表示之特定四羧酸二酐，亦可使用其他四羧酸衍生物之四羧酸、四羧酸二鹵化物、四羧酸二烷酯或四羧酸二烷酯二鹵化物(四羧酸二酐及其衍生物亦統稱為特定四羧酸成份)。 The tetracarboxylic acid component to be used in the production of the specific polymer (A) is preferably a tetracarboxylic dianhydride represented by the following formula [4]. In this case, not only the specific tetracarboxylic dianhydride represented by the formula [4] but also a tetracarboxylic acid, a tetracarboxylic acid dihalide, a dicarboxylic acid dialkyl ester or a tetracarboxylic acid II of another tetracarboxylic acid derivative may be used. Alkyl ester dihalides (tetracarboxylic dianhydrides and derivatives thereof are also collectively referred to as specific tetracarboxylic acid components).

(式[4]中，Z表示由下述式[4a]~式[4q]所成之群所選出之至少1種)。 (In the formula [4], Z represents at least one selected from the group consisting of the following formulas [4a] to [4q]).

式[4a]中，Z1~Z4各自獨立表示氫原子、甲基、乙基、丙基、氯原子或苯環。 In the formula [4a], each of Z 1 to Z 4 independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring.

式[4g]中，Z5及Z6各自獨立表示氫原子或甲基。 In the formula [4g], Z 5 and Z 6 each independently represent a hydrogen atom or a methyl group.

式[4]中之Z1，就合成之容易度或製造聚合物之際的聚合反應性之容易性等觀點，以式[4a]、式[4c]~[4g]、式 [4k]~式[4m]或式[4p]為佳，更佳為式[4a]、式[4e]~式[4g]、式[4l]、式[4m]或式[4p]。特佳為式[4a]、式[4e]、式[4f]、式[4l]、式[4m]或式[4p]。 Z 1 in the formula [4] is expressed by the formula [4a], the formula [4c] to the [4g], and the formula [4k] in terms of easiness of synthesis or easiness of polymerization reactivity at the time of producing a polymer. The formula [4m] or the formula [4p] is preferred, and more preferably the formula [4a], the formula [4e] to the formula [4g], the formula [4l], the formula [4m] or the formula [4p]. Particularly preferred is the formula [4a], the formula [4e], the formula [4f], the formula [4l], the formula [4m] or the formula [4p].

更具體而言，可列舉如，以下述式[4a-1]或式[4a-2]為佳。 More specifically, for example, the following formula [4a-1] or formula [4a-2] is preferred.

特定聚合物(A)及(B)中之特定四羧酸成份，於全部之四羧酸成份100莫耳%中，以50~100莫耳%為佳，以70~100莫耳%為較佳，特佳為80~100莫耳%。 The specific tetracarboxylic acid component in the specific polymers (A) and (B) is preferably 50 to 100 mol%, and 70 to 100 mol%, based on 100 mol% of the total tetracarboxylic acid component. Good, especially good for 80~100%.

特定四羧酸成份，於配合特定聚合物(A)對溶劑之溶解性或液晶配向劑之塗佈性、作為液晶配向膜之情形中的液晶之配向性、電壓保持率、蓄積電荷等特性，可使用1種類或將2種類以上混合使用。 The specific tetracarboxylic acid component is blended with the solubility of the specific polymer (A) in the solvent or the coating property of the liquid crystal alignment agent, the alignment property of the liquid crystal in the case of the liquid crystal alignment film, the voltage retention ratio, and the charge accumulation. One type or two types or more can be used in combination.

特定聚合物(A)之聚醯亞胺系聚合物中，於無損本發明效果之範圍內，可使用特定四羧酸成份以外的其他之四羧酸成份。 In the polyamidene-based polymer of the specific polymer (A), other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used within the range which does not impair the effects of the present invention.

該其他之四羧酸成份，可列舉如，下述四羧酸化合物、四羧酸二酐、四羧酸二鹵化物、四羧酸二烷酯或四羧酸二烷酯二鹵化物等。 Examples of the other tetracarboxylic acid component include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalides, dicarboxylic acid dialkyl esters or tetracarboxylic acid dialkyl ester dihalides.

該其他之四羧酸成份，具體而言為，1,2,5,6-萘四羧酸、1,4,5,8-萘四羧酸、1,2,5,6-蒽四羧酸、3,3’,4,4’-聯苯基四羧酸、2,3,3’,4-聯苯基四羧酸、雙(3,4-二羧基苯 基)醚、3,3’,4,4’-二苯甲酮四羧酸、雙(3,4-二羧基苯基)碸、雙(3,4-二羧基苯基)甲烷、2,2-雙(3,4-二羧基苯基)丙烷、1,1,1,3,3,3-六氟-2,2-雙(3,4-二羧基苯基)丙烷、雙(3,4-二羧基苯基)二甲基矽烷、雙(3,4-二羧基苯基)二苯基矽烷、2,3,4,5-吡啶四羧酸、2,6-雙(3,4-二羧基苯基)吡啶、3,3’,4,4’-二苯基碸四羧酸、3,4,9,10-苝四羧酸、1,3-二苯基-1,2,3,4-環丁烷四羧酸等。該其他之四羧酸成份可使用1種或將2種以上混合使用。 The other tetracarboxylic acid component, specifically, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-fluorene tetracarboxylic acid Acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxybenzene Ether, 3,3',4,4'-benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)methane, 2, 2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, double (3 , 4-dicarboxyphenyl)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3, 4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10-decanetetracarboxylic acid, 1,3-diphenyl-1, 2,3,4-cyclobutanetetracarboxylic acid, and the like. These other tetracarboxylic acid components may be used alone or in combination of two or more.

<特定聚合物(B)> <Specific polymer (B)>

本發明之液晶配向劑為含有，由含有下述式(B-1)所表示之四羧酸二酐之四羧酸成份與含有下述式(B-2)所表示之二胺的二胺成份經聚縮合反應而製得之聚醯胺酸及該聚醯胺酸之醯亞胺化聚合物所成之群所選出之至少1種的聚合物與有機溶劑。 The liquid crystal alignment agent of the present invention contains a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (B-1) and a diamine containing a diamine represented by the following formula (B-2). At least one polymer selected from the group consisting of polyglycine prepared by a polycondensation reaction and a ruthenium imidized polymer of the polyaminic acid, and an organic solvent.

式(B-1)所表示之四羧酸二酐之比例，過少時，將無法得到本發明之效果。因此，式(B-1)所表示之四羧酸二酐之比例，相對於全四羧酸二酐1莫耳，以10~100莫耳%為佳，較佳為30~100莫耳%、更佳為50 ~100莫耳%。 When the ratio of the tetracarboxylic dianhydride represented by the formula (B-1) is too small, the effects of the present invention cannot be obtained. Therefore, the ratio of the tetracarboxylic dianhydride represented by the formula (B-1) is preferably from 10 to 100 mol%, more preferably from 30 to 100 mol%, based on 1 mol of the total tetracarboxylic dianhydride. More preferably 50 ~100% by mole.

液晶配向劑所含有之聚醯胺酸，除上述式(B-1)所表示之四羧酸二酐以外，亦可使用下述式(B-3)所表示之四羧酸二酐。 In addition to the tetracarboxylic dianhydride represented by the above formula (B-1), the polycarboxylic acid contained in the liquid crystal alignment agent may be a tetracarboxylic dianhydride represented by the following formula (B-3).

式(B-3)中，X為4價之有機基，其結構並未有特別之限定。列舉具體例時，可列舉如，下述式(X-1)~式(X-42)。 In the formula (B-3), X is a tetravalent organic group, and the structure thereof is not particularly limited. In the case of a specific example, the following formula (X-1) to formula (X-42) can be mentioned.

式(X-1)中，R3~R6各自獨立表示氫原子、碳數1~6之烷基，或苯基，又以氫原子，或甲基為較佳。 In the formula (X-1), R 3 to R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and a hydrogen atom or a methyl group is preferred.

就化合物之容易取得性之觀點，四羧酸二酐以由下述 式(B-4)所表示之結構所成之群所選出之至少1種為佳。 From the viewpoint of easy availability of the compound, the tetracarboxylic dianhydride is as follows At least one selected from the group consisting of the structures represented by the formula (B-4) is preferred.

(式[B-4]中，X1為由上述式(X-1)~式(X-14)所表示之結構所成之群所選出之至少1種)。 (In the formula [B-4], X 1 is at least one selected from the group consisting of the structures represented by the above formulas (X-1) to (X-14)).

就更提高所得液晶配向膜之信賴性之觀點，X1以僅由上述式(X-1)~式(X-7)及式(X-11)般脂肪族基所構成之結構(亦可含有氧原子)為佳，以式(X-1)之結構為較佳。此外，就顯示出良好液晶配向性之觀點，X1之結構以下述式(X1-1)或式(X1-2)為更佳。 From the viewpoint of further improving the reliability of the obtained liquid crystal alignment film, X 1 has a structure composed only of the aliphatic groups such as the above formula (X-1) to formula (X-7) and formula (X-11) (may also Preferably, an oxygen atom is contained, and a structure of the formula (X-1) is preferred. Further, from the viewpoint of exhibiting good liquid crystal alignment, the structure of X 1 is preferably the following formula (X1-1) or formula (X1-2).

式(B-3)所表示之四羧酸二酐之比例過多時，因會有損害本發明之效果的可能性，故為不佳。因此，式(B-3)所表示之四羧酸二酐之比例，相對於全四羧酸二酐1莫耳，以0~90莫耳%為佳，較佳為0~70莫耳%、更佳為0~50莫耳%。 When the ratio of the tetracarboxylic dianhydride represented by the formula (B-3) is too large, the effect of the present invention may be impaired, which is not preferable. Therefore, the ratio of the tetracarboxylic dianhydride represented by the formula (B-3) is preferably 0 to 90 mol%, more preferably 0 to 70 mol%, based on 1 mol of the total tetracarboxylic dianhydride. More preferably, it is 0~50% by mole.

式(B-2)中，Y1為具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構的2價之有機基，B1 及B2各自獨立表示氫原子、碳數1~10之烷基、碳數1~10之烯基，或碳數1~10之炔基，該些之基可具有取代基。 In the formula (B-2), Y 1 is a divalent organic group having at least one structure selected from the group consisting of an amine group, an imine group, and a nitrogen-containing hetero ring, and each of B 1 and B 2 It independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, and these groups may have a substituent.

該些之基，與前述式[1-1]中之A1及A2中之定義為相同，較佳之例示亦為相同之意義。 The basis of these is the same as defined in A 1 and A 2 in the above formula [1-1], and the preferred examples are also of the same meaning.

一般而言，導入高體積密度之結構時，因會有降低胺基之反應性或液晶配向性之可能性，故B1及B2以氫原子，或可具有取代基之碳數1~5之烷基為較佳，以氫原子、甲基或乙基為特佳。 In general, when a structure having a high bulk density is introduced, B 1 and B 2 may have a hydrogen atom or a carbon number of 1 to 5 which may have a substituent because of the possibility of lowering the reactivity of the amine group or the liquid crystal alignment property. The alkyl group is preferably a hydrogen atom, a methyl group or an ethyl group.

式(B-2)中之Y1，具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構時，該有機基並無需特別之限定。具體例如，具有由下述式(YD-1)~式(YD-5)所表示之胺基、亞胺基，及含氮雜環所成之群所選出之至少1種之結構的2價之有機基等。 When Y 1 in the formula (B-2) has a structure selected from at least one selected from the group consisting of an amine group, an imine group, and a nitrogen-containing hetero ring, the organic group is not particularly limited. Specifically, for example, a divalent structure having at least one selected from the group consisting of an amine group represented by the following formula (YD-1) to formula (YD-5), an imine group, and a nitrogen-containing heterocyclic ring Organic base and the like.

式(YD-1)中，E1為碳數3~15之含氮原子之雜環，Q1為氫原子，或可具有取代基之碳數1~20之 烴基。 In the formula (YD-1), E 1 is a heterocyclic ring containing a nitrogen atom having 3 to 15 carbon atoms, and Q 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

式(YD-2)中，W1為碳數1~10之烴基，E2為具有含氮原子之雜環的碳數3~15之1價之有機基，或被碳數1~6之脂肪族基所取代的二取代胺基。 In the formula (YD-2), W 1 is a hydrocarbon group having 1 to 10 carbon atoms, and E 2 is a monovalent organic group having a carbon number of 3 to 15 having a hetero ring containing a nitrogen atom, or a carbon number of 1 to 6 A disubstituted amine group substituted with an aliphatic group.

式(YD-3)中，W2為碳數6~15，且具有1~2個苯環之2價之有機基，W3為碳數2~5之伸烷基或伸聯苯基，Q2為氫原子、碳數1~5之烷基，或苯環，a為0~1之整數。 In the formula (YD-3), W 2 is a carbon number of 6 to 15, and has a divalent organic group of 1 to 2 benzene rings, and W 3 is an alkylene group having 2 to 5 carbon atoms or a stretched biphenyl group. Q 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a benzene ring, and a is an integer of 0 to 1.

式(YD-4)中，E3為碳數3~15之含氮原子之雜環。 In the formula (YD-4), E 3 is a heterocyclic ring containing a nitrogen atom having 3 to 15 carbon atoms.

式(YD-5)中，E4為碳數3~15之含氮原子之雜環，W5為碳數2~5之伸烷基。 In the formula (YD-5), E 4 is a heterocyclic ring containing a nitrogen atom having 3 to 15 carbon atoms, and W 5 is an alkylene group having 2 to 5 carbon atoms.

式(YD-1)、式(YD-2)、式(YD-4)，及式(YD-5)之E1、E2、E3，及E4之碳數3~15之含氮原子之雜環，只要為公知之結構者，則未有特別限定之內容。其中，可列舉如，吡咯、吡咯、咪唑、吡唑、噁唑、噻唑、哌啶、哌、吡啶、吡、吲哚、苯併咪唑、喹啉、異喹啉等，又以哌、哌啶、吲哚、苯併咪唑、咪唑、咔唑，或吡啶為較佳。 Formula (YD-1), formula (YD-2), formula (YD-4), and formula (YD-5) E 1 , E 2 , E 3 , and E 4 have a carbon number of 3 to 15 nitrogen The heterocyclic ring of an atom is not particularly limited as long as it is a well-known structure. Among them, pyrrole , pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine Pyridine, pyridyl , hydrazine, benzimidazole, quinoline, isoquinoline, etc. Preferably, piperidine, hydrazine, benzimidazole, imidazole, oxazole, or pyridine is preferred.

此外，式(B-2)中之Y1之具體例，可列舉如，具有下述式(YD-6)~式(YD-21)所表示之氮原子的2價之有機基。就可抑制因交流驅動所造成之電荷蓄積之觀點，以式(YD-14)~式(YD-21)為較佳，以式(YD-14)或式(YD-18)為特佳。 In addition, specific examples of Y 1 in the formula (B-2) include a divalent organic group having a nitrogen atom represented by the following formula (YD-6) to formula (YD-21). From the viewpoint of suppressing the charge accumulation caused by the AC drive, the formula (YD-14) to the formula (YD-21) is preferable, and the formula (YD-14) or the formula (YD-18) is particularly preferable.

式(YD-17)中，h為1~3之整數，式(YD-14)及式(YD-21)中，j為0~3之整數。 In the formula (YD-17), h is an integer of 1 to 3, and in the formula (YD-14) and the formula (YD-21), j is an integer of 0 to 3.

本發明之聚醯胺酸及該聚醯胺酸之醯亞胺化聚合物中，式(B-2)所表示之二胺之比例，相對於全二 胺1莫耳，以10~100莫耳%為佳，較佳為30~100莫耳%、更佳為50~100莫耳%。 In the polyamiled acid of the present invention and the ruthenium imidized polymer of the polyaminic acid, the ratio of the diamine represented by the formula (B-2) is relative to the total two The amine 1 mole is preferably from 10 to 100 mol%, more preferably from 30 to 100 mol%, still more preferably from 50 to 100 mol%.

本發明之液晶配向劑所含有之聚醯胺酸，除上述式(B-2)所表示之二胺以外，亦可使用下述式(B-5)所表示之二胺。 The polyamine contained in the liquid crystal alignment agent of the present invention may be a diamine represented by the following formula (B-5) in addition to the diamine represented by the above formula (B-2).

下述式(B-5)中之Y2為2價之有機基，其結構並未有特別之限定，亦可為2種類以上混合者。列舉具體例時，可列舉如，下述式(Y-1)~式(Y-76)所表示之結構之2價之有機基等。下述式(B-5)中之B1及B2，包含較佳之例示，為與式(B-2)之B1及B2為相同之定義。 Y 2 in the following formula (B-5) is a divalent organic group, and the structure thereof is not particularly limited, and may be a mixture of two or more types. In the case of a specific example, a divalent organic group or the like having a structure represented by the following formula (Y-1) to formula (Y-76) can be given. B 1 and B 2 in the following formula (B-5), which are preferably exemplified, are the same definitions as B 1 and B 2 of the formula (B-2).

其中，就得到良好的液晶配向性之觀點，又以高直線性之二胺為佳，Y2，以具有式(Y-7)、式(Y-21)~式(Y-23)、式(Y-25)~式(Y-27)、式(Y-43)~式(Y-46)、式(Y-48)、式(Y-63)、式(Y-71)，或式(Y-73)~式(Y-76)所表示之2價之有機基 之二胺為佳。 Among them, from the viewpoint of obtaining good liquid crystal alignment, it is preferable to use a highly linear diamine, and Y 2 has a formula (Y-7), a formula (Y-21), a formula (Y-23), and a formula. (Y-25)~(Y-27), (Y-43)~(Y-46), Y-48, Y-63, Y-71, or (Y-73) is preferably a divalent organic diamine represented by the formula (Y-76).

式(B-5)所表示之二胺之比例過多時，因會有損及本發明效果之可能性，而為不佳。因此，式(B-5)所表示之二胺之比例，相對於全二胺1莫耳，以0~90莫耳%為佳，較佳為0~70莫耳%、更佳為0~50莫耳%。 When the ratio of the diamine represented by the formula (B-5) is too large, the possibility of the effect of the present invention may be impaired, which is not preferable. Therefore, the ratio of the diamine represented by the formula (B-5) is preferably 0 to 90 mol%, more preferably 0 to 70 mol%, more preferably 0 to 0% with respect to the total diamine 1 mol. 50% by mole.

<特定聚合物(A)及特定聚合物(B)之製造方法> <Method for Producing Specific Polymer (A) and Specific Polymer (B)>

本發明中，製造特定聚合物(A)及特定聚合物(B)之方法並未有特別之限定。通常可使二胺成份與四羧酸成份反應而得之。一般而言為，使由四羧酸二酐及其四羧酸之衍生物所成之群所選出之至少1種的四羧酸成份，與1種或多數種之二胺所形成之二胺成份進行反應，而製得聚醯胺酸之方法等。具體而言，例如可使用使四羧酸二酐與一級或二級的二胺進行縮合而以製得聚醯胺酸之方法、使四羧酸與一級或二級的二胺經脫水聚縮合反應而製得聚醯胺酸之方法，或使四羧酸二鹵化物與一級或二級的二胺進行聚縮合而製得聚醯胺酸之方法。 In the present invention, the method of producing the specific polymer (A) and the specific polymer (B) is not particularly limited. It is usually obtained by reacting a diamine component with a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and a derivative of a tetracarboxylic acid, and a diamine formed from one or a plurality of diamines A method in which a component is reacted to obtain a polyamido acid or the like. Specifically, for example, a method in which a tetracarboxylic dianhydride is condensed with a primary or secondary diamine to obtain a polyamic acid, and a tetracarboxylic acid and a primary or secondary diamine may be subjected to dehydration polymerization. A method of producing a poly-proline by reacting, or a method of polycondensing a tetracarboxylic acid dihalide with a primary or secondary diamine to obtain a poly-proline.

欲製得聚醯胺酸烷酯之方法中，可使用羧酸基經二烷酯化之四羧酸與一級或二級的二胺進行聚縮合之方法、使羧酸基經二烷酯化之四羧酸二鹵化物與一級或二級的二胺進行聚縮合之方法，或使聚醯胺酸之羧基變換為酯之方法等。 In the method for producing a polyalkyl amide, a method in which a carboxylic acid group is subjected to polycondensation of a dialkyl esterified tetracarboxylic acid with a primary or secondary diamine, and a carboxylic acid group is dialkyl esterified. A method of polycondensing a tetracarboxylic acid dihalide with a primary or secondary diamine, or a method of converting a carboxyl group of a polylysine to an ester.

製得聚醯亞胺之方法中，為使用使前述聚醯胺酸或聚醯胺酸烷酯閉環形成聚醯亞胺之方法。 In the method for producing a polyimine, a method of forming a polyimine by ring-closing the polyamic acid or polyalkyl amide is used.

二胺成份與四羧酸成份之反應，通常為於溶劑中進行。此時所使用之溶劑，只要可溶解所生成之聚醯亞胺前驅物者時，並未有特別之限定。下述為列舉反應所使用的溶劑之具體例，但並非限定於該些之例示中。 The reaction of the diamine component with the tetracarboxylic acid component is usually carried out in a solvent. The solvent to be used at this time is not particularly limited as long as it can dissolve the produced polyimide precursor. The following are specific examples of the solvent used for the reaction, but are not limited to the examples.

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、二甲基亞碸或1,3-二甲基-四氫咪唑酮等。又，聚醯亞胺前驅物之溶劑溶解性較高之情形，可使用甲基乙基酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮或下述式[D-1]~式[D-3]所表示之溶劑。 For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamidine An amine, dimethyl hydrazine or 1,3-dimethyl-tetrahydroimidazolidone or the like. Further, in the case where the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula may be used. [D-1]~ The solvent represented by the formula [D-3].

(式[D-1]中，D1表示碳數1~3之烷基，式[D-2]中，D2表示碳數1~3之烷基，式[D-3]中，D3表示碳數1~4之烷基)。 (In the formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D 2 represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D 3 represents an alkyl group having 1 to 4 carbon atoms).

該些之溶劑可單獨使用亦可、混合使用亦可。此外，即使為不能溶解聚醯亞胺前驅物之溶劑，只要不會析出所生成之聚醯亞胺前驅物之範圍，亦可與前述溶劑混合使用。又，溶劑中之水份，為阻礙聚合反應，此外，也為造成使所生成之聚醯亞胺前驅物水解之原因，故溶劑以使用脫水乾燥者為佳。 These solvents may be used singly or in combination. Further, even a solvent which cannot dissolve the polyimide precursor can be used in combination with the solvent as long as the range of the produced polyimide precursor is not precipitated. Further, the water content in the solvent is a factor which hinders the polymerization reaction, and also causes the hydrolysis of the produced polyimide precursor, so that the solvent is preferably dried by dehydration.

二胺成份與四羧酸成份於溶劑中進行反應之際，可列 舉如，於使二胺成份分散於溶劑中或將溶解所得後之溶液於攪拌中，添加四羧酸成份，或分散或溶解於溶劑中之方法、相反地或使四羧酸成份分散於溶劑中，或於溶解之溶液中添加二胺成份之方法、交互添加二胺成份與四羧酸成份之方法等，而可使用該些任一之方法。又，分別使用多數種二胺成份或四羧酸成份進行反應之情形，可於預先混合之狀態下進行反應亦可、各別地依序反應亦可、或再與各別反應之低分子量體進行混合反應形成聚合物亦可。 When the diamine component reacts with the tetracarboxylic acid component in a solvent, it can be listed. For example, a method in which a diamine component is dispersed in a solvent or a solution obtained by dissolving the obtained solution is stirred, a tetracarboxylic acid component is added, or a method of dispersing or dissolving in a solvent, or a tetracarboxylic acid component is dispersed in a solvent. In either, a method of adding a diamine component to the dissolved solution, a method of alternately adding a diamine component and a tetracarboxylic acid component, or the like may be used. Further, in the case where a reaction is carried out using a plurality of kinds of diamine components or tetracarboxylic acid components, respectively, the reaction may be carried out in a state of being premixed, or may be separately reacted in sequence, or may be further reacted with a low molecular weight body. It is also possible to carry out a mixed reaction to form a polymer.

此時之聚合溫度可選擇於-20~150℃中之任意溫度，較佳為-5~100℃之範圍。 The polymerization temperature at this time may be selected from any of -20 to 150 ° C, preferably from -5 to 100 ° C.

又，反應可以任意之濃度進行，濃度過低時將無法得到高分子量之聚合物，濃度過高時將會過度增加反應液之黏性，而於無法均勻地攪拌。因此，較佳為1~50質量%、更佳為5~30質量%。反應初期以高濃度進行，其後，再追加溶劑亦可。 Further, the reaction can be carried out at any concentration. When the concentration is too low, a polymer having a high molecular weight cannot be obtained. When the concentration is too high, the viscosity of the reaction liquid is excessively increased, and the mixture cannot be uniformly stirred. Therefore, it is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and thereafter, a solvent may be added.

聚醯亞胺前驅物之聚合反應中，二胺成份之合計莫耳數與四羧酸成份之合計莫耳數之比以0.8~1.2為佳。與一般之聚縮合反應相同般，該莫耳比越接近1.0時，表示所生成之聚醯亞胺前驅物的分子量越大。 In the polymerization of the polyimine precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

聚醯亞胺為前述聚醯亞胺前驅物經閉環而得之聚醯亞胺，該聚醯亞胺中，醯胺酸基之閉環率(亦稱為醯亞胺化率)並非必須為100%，其可配合用途或目的進行任意之調整。 Polyimine is a polyimine obtained by ring closure of the aforementioned polyimide precursor. In the polyimine, the ring closure ratio (also referred to as oxime imidization ratio) of the amidino group is not necessarily 100. %, which can be adjusted to suit the purpose or purpose.

使聚醯亞胺前驅物醯亞胺化之方法，可列舉如，使聚 醯亞胺前驅物之溶液加熱之熱醯亞胺化之方法，或於聚醯亞胺前驅物之溶液中添加觸媒以進行觸媒醯亞胺化之方法等。 A method for imidating a polyimine precursor precursor, for example, to polymerize A method of heat-imiding imidization of a solution of a ruthenium imine precursor, or a method of adding a catalyst to a solution of a polyimide precursor to carry out catalytic imidization.

聚醯亞胺前驅物於溶液中進行熱醯亞胺化之情形的溫度為100~400℃、較佳為120~250℃，以將醯亞胺化反應所生成之水排出於反應系外中進行者為佳。 The temperature at which the polyimine precursor is thermally imidized in the solution is 100 to 400 ° C, preferably 120 to 250 ° C, to discharge the water formed by the hydrazine imidization reaction into the reaction system. The performer is better.

聚醯亞胺前驅物之觸媒醯亞胺化，可於聚醯亞胺前驅物之溶液中，添加鹼性觸媒與酸酐後，於-20~250℃、較佳為0~180℃下，以攪拌之方式進行。 The catalyst of the polyimine precursor is imidized, and after adding a basic catalyst and an acid anhydride in the solution of the polyimide precursor, at -20 to 250 ° C, preferably 0 to 180 ° C , by stirring.

鹼性觸媒之量為，醯胺酸基之0.5~30莫耳倍、較佳為2~20莫耳倍，酸酐之量為，醯胺酸基之1~50莫耳倍、較佳為3~30莫耳倍。 The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles.

鹼性觸媒可列舉如，吡啶、三乙基胺、三甲基胺、三丁基胺、三辛基胺等。其中，又以吡啶於反應進行中可維持適當之鹼性，而為較佳。 Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferably used in the course of the reaction to maintain an appropriate basicity.

酸酐可列舉如，乙酸酐、偏苯三甲酸酐、苯均四酸酐等。其中，又以使用乙酸酐時，於反應結束後容易進行精製而為較佳。 Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, when acetic anhydride is used, it is preferred to carry out purification after completion of the reaction.

觸媒醯亞胺化之醯亞胺化率，可以調節觸媒量與反應溫度、反應時間之方式予以控制。 The imidization rate of the imidization of the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

由聚醯亞胺前驅物或聚醯亞胺之反應溶液中，回收所生成之聚醯亞胺前驅物或聚醯亞胺之情形，只要將反應溶液投入溶劑中，使其沈澱即可。沈澱所使用的溶劑，可列舉如，甲醇、乙醇、異丙醇、丙酮、己烷、丁基溶纖劑、 庚烷、甲基乙基酮、甲基異丁酮、甲苯、苯、水等。投入溶劑後沈澱之聚合物，可於過濾、回收之後，於常壓或減壓下，以常溫或加熱進行乾燥。又，沈澱後回收的聚合物，於進行2次~10次重複再溶解於溶劑、再沈澱回收之操作後，即可降低聚合物中之雜質。此時之溶劑，可列舉如，醇類、酮類、烴等。使用3種類以上由該些之中所選出之溶劑時，以其可更提高精製之效率而為較佳。 In the case where the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, the reaction solution may be added to a solvent to precipitate. Examples of the solvent used for the precipitation include methanol, ethanol, isopropanol, acetone, hexane, and butyl cellosolve. Heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. The polymer precipitated after the solvent is introduced may be filtered, recovered, and dried at normal temperature or under a normal pressure or a reduced pressure. Further, the polymer recovered after the precipitation can be reduced in the polymer by repeating the re-dissolution in the solvent and reprecipitation recovery after 2 to 10 repetitions. The solvent at this time may, for example, be an alcohol, a ketone or a hydrocarbon. When three or more types of solvents selected from the above are used, it is preferable to further improve the efficiency of purification.

本發明中，特定聚合物(A)及(B)中，以使用聚醯胺酸烷酯為佳。 In the present invention, it is preferred to use a polyalkylene amide in the specific polymers (A) and (B).

製造本發明之聚醯胺酸烷酯時，更具體之方法係如下述(1)~(3)所示。 When the polyalkyl amide of the present invention is produced, a more specific method is as shown in the following (1) to (3).

(1)以聚醯胺酸之酯化反應製造之方法 (1) A method for producing an esterification reaction of polyproline

由二胺成份與四羧酸成份製造聚醯胺酸，使其於該羧基(COOH基)上，進行化學反應，即酯化反應，以製造聚醯胺酸烷酯之方法。 A method in which a polyaminic acid is produced from a diamine component and a tetracarboxylic acid component to carry out a chemical reaction, that is, an esterification reaction, on the carboxyl group (COOH group) to produce a polyalkylenimine.

酯化反應為，使聚醯胺酸與酯化劑於溶劑之存在下，於-20~150℃(較佳為0~50℃)中，進行30分~24小時(較佳為1~4小時)反應之方法。 The esterification reaction is carried out by allowing the polyaminic acid and the esterifying agent to be carried out in the presence of a solvent at -20 to 150 ° C (preferably 0 to 50 ° C) for 30 minutes to 24 hours (preferably 1 to 4). Hours) Method of reaction.

前述酯化劑，以於酯化反應後容易去除者為佳，以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-甲苯基三氮烯、1-乙基-3-p-甲苯基三氮 烯、1-丙基-3-p-甲苯基三氮烯、4-(4,6-二甲氧基-1,3,5-三-2-基)-4-甲基嗎福啉氯化物等。酯化劑之使用量，相對於聚醯胺酸之重複單位1莫耳，以2~6莫耳當量為佳。其中又以2~4莫耳當量為佳。 The esterifying agent is preferably removed after the esterification reaction, and N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dineopentyl butyl acetal, N,N-dimethylformamide di-t-butyl Acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene, 4 -(4,6-dimethoxy-1,3,5-three -2-yl)-4-methylmorpholine chloride and the like. The amount of the esterifying agent to be used is preferably 2 to 6 moles per equivalent of the repeating unit of polylysine. Among them, 2 to 4 molar equivalents are preferred.

前述酯化反應所使用的溶劑，就聚醯胺酸對溶劑之溶解性之觀點，可列舉如，前述二胺成份與四羧酸成份反應時所使用的溶劑等。其中又以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮或γ-丁內酯為佳。該些溶劑，可使用1種或將2種以上混合使用亦可。 The solvent used for the esterification reaction is, for example, a solvent used for the reaction of the diamine component with a tetracarboxylic acid component, from the viewpoint of the solubility of the polyaminic acid in the solvent. Among them, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferred. These solvents may be used alone or in combination of two or more.

前述酯化反應中之溶劑中之聚醯胺酸的濃度，就不易引起聚醯胺酸之析出之觀點，以1~30質量%為佳。其中又以5~20質量%為佳。 The concentration of the polyglycolic acid in the solvent in the esterification reaction is less likely to cause precipitation of polyglycine, and is preferably from 1 to 30% by mass. Among them, 5 to 20% by mass is preferred.

(2)使二胺成份與四羧酸二酯二氯化物進行反應以製造之方法 (2) A method of reacting a diamine component with a tetracarboxylic acid diester dichloride to produce

具體而言，為使二胺成份與四羧酸二酯二氯化物於鹼與溶劑之存在下，於-20~150℃(較佳為0~50℃)中，進行30分鐘~24小時(較佳為1~4小時)反應之方法。 Specifically, in order to make the diamine component and the tetracarboxylic acid diester dichloride in the presence of a base and a solvent, it is carried out at -20 to 150 ° C (preferably 0 to 50 ° C) for 30 minutes to 24 hours ( Preferably, the method of reaction is 1 to 4 hours.

鹼，可使用吡啶、三乙基胺、4-二甲基胺基吡啶等。其中，就反應可穩定進行之觀點，以使用吡啶為佳。鹼之使用量，以可於反應後容易去除之量為佳，相對於四羧酸二酯二氯化物，以2~4倍莫耳為佳。其中，又以2~3倍 莫耳為較佳。 As the base, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used. Among them, in view of the fact that the reaction can be stably carried out, it is preferred to use pyridine. The amount of the base to be used is preferably an amount which can be easily removed after the reaction, and is preferably 2 to 4 times the molar amount based on the tetracarboxylic acid diester dichloride. Among them, it is 2~3 times Moore is preferred.

溶劑，就所製得之聚合物，即聚醯胺酸烷酯對溶劑之溶解性之觀點，例如可使用前述二胺成份與四羧酸成份反應時所使用的溶劑等。其中，又以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮或γ-丁內酯為佳。該些之溶劑，可使用1種或將2種以上混合使用亦可。 The solvent, for example, a solvent used for the reaction of the polymer of the polyamidamide with a solvent, for example, a solvent used when the diamine component and the tetracarboxylic acid component are reacted can be used. Among them, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferred. These solvents may be used alone or in combination of two or more.

反應中之溶劑中之聚醯胺酸烷酯的濃度，就不易析出聚醯胺酸烷酯之觀點，以1~30質量%為佳。其中，又以5~20質量%為佳。又，為防止四羧酸二酯二氯化物之水解，製作聚醯胺酸烷酯時所使用的溶劑，以盡量使用脫水者為佳。此外，反應為於氮氣雰圍中，以避免外氣混入者為佳。 The concentration of the polyalkyl amide in the solvent in the reaction is less likely to precipitate the polyalkyl amide, and is preferably from 1 to 30% by mass. Among them, 5 to 20% by mass is preferred. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferred to use a solvent which is used in the production of polyalkyl amide. Further, the reaction is carried out in a nitrogen atmosphere to avoid the incorporation of outside air.

(3)使二胺成份與四羧酸二酯進行反應之製造方法 (3) A method for producing a reaction between a diamine component and a tetracarboxylic acid diester

具體而言，為將二胺成份與四羧酸二酯，於縮合劑、鹼及溶劑之存在下，於0~150℃(較佳為0~100℃)中，進行30分鐘~24小時(較佳為3~15小時)聚縮合反應之方法。 Specifically, the diamine component and the tetracarboxylic acid diester are carried out in the presence of a condensing agent, a base and a solvent at 0 to 150 ° C (preferably 0 to 100 ° C) for 30 minutes to 24 hours ( Preferably, the method of polycondensation is carried out for 3 to 15 hours.

縮合劑，例如可使用三苯基亞磷酸酯、二環己基羰二醯亞胺、1-乙基-3-(3-二甲基胺基丙基)羰二醯亞胺鹽酸鹽、N,N’-羰基二咪唑、二甲氧基-1,3,5-三基甲基嗎福啉、O-(苯併***-1-基)-N,N,N’,N’-四甲基脲四氟硼酯、O-(苯併***-1-基)-N,N,N’,N’-四甲基脲六氟亞磷 酸酯、(2,3-二氫-2-硫氧-3-苯併噁唑基)膦酸二苯基等。縮合劑之使用量，相對於四羧酸二酯，以2~3倍莫耳為佳，特別是以2~2.5倍莫耳為佳。 As the condensing agent, for example, triphenylphosphite, dicyclohexylcarbonyldiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride, N can be used. , N'-carbonyldiimidazole, dimethoxy-1,3,5-three Methylmorpholine, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl -N,N,N',N'-tetramethyluron hexafluorophosphite, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate, and the like. The amount of the condensing agent used is preferably 2 to 3 moles per mole of the tetracarboxylic acid diester, particularly preferably 2 to 2.5 moles.

鹼，可使用吡啶、三乙基胺等三級胺。鹼之使用量，以於聚縮合反應後容易去除之量為佳，相對於二胺成份，以2~4倍莫耳為佳，以2~3倍莫耳為較佳。 As the base, a tertiary amine such as pyridine or triethylamine can be used. The amount of the base to be used is preferably such that it is easily removed after the polycondensation reaction, and is preferably 2 to 4 times moles, more preferably 2 to 3 times moles, based on the diamine component.

聚縮合反應所使用之溶劑，就所得之聚合物，即，聚醯胺酸烷酯對溶劑之溶解性之觀點，可列舉如，前述二胺成份與四羧酸成份反應時所使用的溶劑等。其中，又以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮或γ-丁內酯為佳。該些溶劑，可使用1種或將2種以上混合使用亦可。 The solvent to be used in the polycondensation reaction, and the solvent to be obtained, that is, the solvent used for the reaction of the diamine component with the tetracarboxylic acid component, etc. . Among them, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferred. These solvents may be used alone or in combination of two or more.

又，聚縮合反應中，將路易士酸作為添加劑添加時，可使反應有效率的進行。路易士酸以氯化鋰、溴化鋰等之鹵化鋰為佳。路易士酸之使用量，相對於二胺成份，以0.1~10倍莫耳為佳。其中，又以2.0~3.0倍莫耳為佳。 Further, in the polycondensation reaction, when Lewis acid is added as an additive, the reaction can be efficiently carried out. The Lewis acid is preferably lithium halide such as lithium chloride or lithium bromide. The amount of Lewis acid used is preferably 0.1 to 10 times the molar amount of the diamine component. Among them, 2.0 to 3.0 times more moles is preferred.

由上述(1)~(3)之方法所得之聚醯胺酸烷酯的溶液中，回收聚醯胺酸烷酯之情形，只要將反應溶液投入溶劑中，使其沈澱即可。沈澱所使用的溶劑，可列舉如，水、甲醇、乙醇、2-丙醇、己烷、丁基溶纖劑(cellosolve)、丙酮、甲苯等。投入溶劑後沈澱之聚合物，就去除前述所使用之添加劑、觸媒類等為目的時，以使用上述溶劑進行多數次洗淨操作者為佳。 In the case where the polyalkyl amide is recovered from the solution of the polyalkyl amide obtained by the above methods (1) to (3), the reaction solution may be added to a solvent to precipitate. Examples of the solvent used for the precipitation include water, methanol, ethanol, 2-propanol, hexane, cellosolve, acetone, toluene, and the like. When the polymer precipitated after the solvent is added, for the purpose of removing the additives, catalysts, and the like used as described above, it is preferred to carry out a plurality of washing operations using the above solvent.

過濾、回收之後，聚合物可於常壓或減壓下、常溫或 加熱下進行乾燥。又，可使沈澱回收之聚合物，再溶解於溶劑中，進行2次~10次再沈澱回收之操作，即可降低聚合物中之雜質。 After filtration and recovery, the polymer can be under normal pressure or reduced pressure, at room temperature or Drying is carried out under heating. Further, the polymer recovered by precipitation can be redissolved in a solvent, and the operation of reprecipitation recovery from 2 to 10 times can reduce impurities in the polymer.

聚醯胺酸烷酯，以使用前述(1)或(2)之方法製造者為佳。 The polyalkyl amide is preferably produced by the method of the above (1) or (2).

<液晶配向劑> <Liquid alignment agent>

本發明之液晶配向劑為，形成液晶配向膜(亦稱為樹脂被膜)所使用之塗佈溶液，其為含有特定聚合物(A)、特定聚合物(B)及有機溶劑。 The liquid crystal alignment agent of the present invention is a coating solution used to form a liquid crystal alignment film (also referred to as a resin film), and contains a specific polymer (A), a specific polymer (B), and an organic solvent.

液晶配向劑中之特定聚合物(B)之比例，相對於特定聚合物(A)100質量份，以10~900質量份為佳。其中，又以25~400質量份為佳，較佳為40~250質量份。最佳為60~160質量份。 The proportion of the specific polymer (B) in the liquid crystal alignment agent is preferably from 10 to 900 parts by mass based on 100 parts by mass of the specific polymer (A). Among them, it is preferably 25 to 400 parts by mass, preferably 40 to 250 parts by mass. The optimum is 60 to 160 parts by mass.

本發明之液晶配向劑中之全部的聚合物成份，可全部為本發明之特定聚合物(A)及(B)，再與該些以外的其他之聚合物混合亦可。該些以外的聚合物，可列舉如，不具有特定結構(1A)、特定結構(1B)及特定結構(2)之聚醯亞胺前驅物及聚醯亞胺等。又如，纖維素系聚合物、丙烯酸聚合物、甲基丙烯酸聚合物、聚苯乙烯、聚醯胺或聚矽氧烷等。此時，該些以外的其他之聚合物之含量，相對於特定聚合物(A)及(B)之合計100質量份，為0.5~15質量份。其中，又以1~10質量份為佳。 All of the polymer components in the liquid crystal alignment agent of the present invention may be all of the specific polymers (A) and (B) of the present invention, and may be mixed with other polymers other than the above. Examples of the polymer other than the above may include a polyimine precursor having no specific structure (1A), a specific structure (1B), and a specific structure (2), and a polyimine. Further, for example, a cellulose polymer, an acrylic polymer, a methacrylic polymer, polystyrene, polyamine or polyoxyalkylene. In this case, the content of the polymer other than the above is 0.5 to 15 parts by mass based on 100 parts by mass of the total of the specific polymers (A) and (B). Among them, it is preferably 1 to 10 parts by mass.

又，液晶配向劑中之有機溶劑之含量，以70 ~99.9質量%為佳。該含量，可依液晶配向劑之塗佈方法或作為目的之液晶配向膜之膜厚，作適當之變更。 Moreover, the content of the organic solvent in the liquid crystal alignment agent is 70 ~99.9 mass% is preferred. The content can be appropriately changed depending on the coating method of the liquid crystal alignment agent or the film thickness of the intended liquid crystal alignment film.

液晶配向劑所使用的有機溶劑，只要含有可溶解特定聚合物(A)及特定聚合物(B)之溶劑(亦稱為良溶劑)時，並未有特別之限定。其可列舉如，下述良溶劑的具體例示等，但並非僅限定於該些之例示者。 The organic solvent used for the liquid crystal alignment agent is not particularly limited as long as it contains a solvent (also referred to as a good solvent) capable of dissolving the specific polymer (A) and the specific polymer (B). The specific examples of the following good solvents are exemplified, but are not limited to those exemplified.

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、二甲基亞碸、γ-丁內酯、1,3-二甲基-四氫咪唑酮、甲基乙基酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮等。 For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl Anthracene, γ-butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

其中，又以使用N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮，或γ-丁內酯為佳。 Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone is preferably used.

此外，就特定聚合物(A)及特定聚合物(B)對溶劑具有高溶解性之情形，以使用前述式[D-1]~式[D-3]所表示之溶劑為佳。 Further, in the case where the specific polymer (A) and the specific polymer (B) have high solubility to a solvent, it is preferred to use a solvent represented by the above formula [D-1] to formula [D-3].

本發明之液晶配向劑中之良溶劑，以包含於液晶配向劑的溶劑全體之20~99質量%為佳。其中，又以20~90質量%為佳。較佳為30~80質量%。 The good solvent in the liquid crystal alignment agent of the present invention is preferably 20 to 99% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, 20 to 90% by mass is preferred. It is preferably 30 to 80% by mass.

本發明之液晶配向劑，於無損本發明效果之範圍，可使用於塗佈液晶配向劑之際提高液晶配向膜之塗膜性或表面平滑性之溶劑(亦稱為貧溶劑)。下述為貧溶劑的具體例示，但並非僅限定於該些之例示者。 The liquid crystal alignment agent of the present invention can be used as a solvent (also referred to as a poor solvent) for improving the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment agent is applied, without impairing the effects of the present invention. The following are specific examples of the poor solvent, but are not limited to those exemplified.

例如，乙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、tert-丁醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁 醇、異戊醇、tert-戊醇、3-甲基-2-丁醇、新戊醇、1-己醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己醇、1,2-乙烷二醇、1,2-丙烷二醇、1,3-丙烷二醇、1,2-丁烷二醇、1,3-丁烷二醇、1,4-丁烷二醇、2,3-丁烷二醇、1,5-戊烷二醇、2-甲基-2,4-戊烷二醇、2-乙基-1,3-己烷二醇、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、丙烯碳酸酯、伸乙基碳酸酯、2-(甲氧基甲氧基)乙醇、乙二醇單丁基醚、乙二醇單異戊醚、乙二醇單己基醚、2-(己基氧基)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、伸三乙二醇、伸三乙二醇單甲基醚、三乙二醇 單乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯、前述式[D-1]~[D-3]所表示之溶劑等。 For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butene Alcohol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1 -methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 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-pentanediol, 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 dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methyl Pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethyl carbonate 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, decyl 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, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol single ethyl Acid ester, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl Acid ester, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxyprop Methyl ester, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid Ester, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, the above formula [D-1]~[D-3] The solvent and the like indicated.

其中，又以使用1-己醇、環己醇、1,2-乙烷二醇、1,2-丙烷二醇、丙二醇單丁基醚、乙二醇單丁基醚或二丙二醇二甲基醚為佳。 Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl is used. Ether is preferred.

該些貧溶劑，以包含液晶配向劑的溶劑全體之1~80質量%為佳。其中，又以10~80質量%為佳。較佳為20~70質量%。 The amount of the poor solvent is preferably from 1 to 80% by mass based on the total amount of the solvent containing the liquid crystal alignment agent. Among them, 10 to 80% by mass is preferred. It is preferably 20 to 70% by mass.

本發明之液晶配向劑中，以含有 具有環氧基、異氰酸酯基、環氧丙烷基或環碳酸酯基之交聯性化合物、 由具有羥基、羥烷基及低級烷氧基烷基所成之群所選出之至少1種的取代基之交聯性化合物，或 具有聚合性不飽和鍵結之交聯性化合物為佳。該些取代基或聚合性不飽和鍵結，於交聯性化合物中必須具有2個以上。 In the liquid crystal alignment agent of the present invention, a crosslinkable compound having an epoxy group, an isocyanate group, an oxypropylene group or a cyclic carbonate group, a crosslinkable compound of at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group, or A crosslinkable compound having a polymerizable unsaturated bond is preferred. These substituents or polymerizable unsaturated bonds must have two or more of the crosslinkable compounds.

具有環氧基或異氰酸酯基之交聯性化合物，可列舉如，雙酚丙酮縮水甘油醚、酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、三縮水甘油異三聚氰酸酯、四縮 水甘油胺基伸二苯基、四縮水甘油-m-二甲苯二胺、四縮水甘油-1,3-雙(胺基乙基)環己烷、四苯基縮水甘油醚乙烷、三苯基縮水甘油醚乙烷、雙酚六氟丙酮二縮水甘油醚、1,3-雙(1-(2,3-環氧丙氧基)-1-三氟甲基-2,2,2-三氟甲基)苯、4,4-雙(2,3-環氧丙氧基)八氟聯苯基、三縮水甘油-p-胺基酚、四縮水甘油甲基二甲苯二胺、2-(4-(2,3-環氧丙氧基)苯基)-2-(4-(1,1-雙(4-(2,3-環氧丙氧基)苯基)乙基)苯基)丙烷、1,3-雙(4-(1-(4-(2,3-環氧丙氧基)苯基)-1-(4-(1-(4-(2,3-環氧丙氧基)苯基)-1-甲基乙基)苯基)乙基)苯氧基)-2-丙醇等。 Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, and the like. Shrink Glycidylamine diphenyl, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl ether ethane, triphenyl Glycidyl ether ethane, bisphenol hexafluoroacetone diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-three Fluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidylmethylxylenediamine, 2- (4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)benzene Propane, 1,3-bis(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-(4-(1-(4-(2,3-) ring) Oxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol and the like.

具有環氧丙烷基之交聯性化合物，為至少具有2個下述式[4A]所示環氧丙烷基之交聯性化合物。 The crosslinkable compound having an oxypropylene group is a crosslinkable compound having at least two oxypropylene groups represented by the following formula [4A].

具體而言，可列舉如，國際公開公報WO2011/132751(2011.10.27公開)之58~59頁所揭示之式[4a]~[4k]所表示之交聯性化合物等。 Specifically, a crosslinkable compound represented by the formulas [4a] to [4k] disclosed in pages 58 to 59 of International Publication WO2011/132751 (2011.10.27 publication) can be mentioned.

具有環碳酸酯基之交聯性化合物，為至少具有2個下述式[5A]所表示之環碳酸酯基之交聯性化合物。 The crosslinkable compound having a cyclic carbonate group is a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [5A].

具體而言，可列舉如，國際公開公報WO2012/014898 (2012.2.2公開)之76~82頁所揭示之式[5-1]~[5-42]所表示之交聯性化合物等。 Specifically, for example, International Publication WO2012/014898 A crosslinkable compound represented by the formula [5-1] to [5-42] disclosed in pages 76 to 82 of (2012.2.2 publication).

具有由羥基及烷氧基所成之群所選出之至少1種的取代基之交聯性化合物，例如，具有羥基或烷氧基之胺基樹脂例如，三聚氰胺樹脂、脲樹脂、呱樹脂、乙炔脲-甲醛樹脂、琥珀醯胺-甲醛樹脂、乙烯脲-甲醛樹脂等。具體而言為，胺基之氫原子被羥甲基及/或烷氧基甲基所取代的三聚氰胺衍生物、苯併呱衍生物，或可使用乙炔脲等。該三聚氰胺衍生物或苯併呱衍生物，可以二聚物或三聚物方式存在。該些相當於1個三環以具有平均3個以上6個以下之羥甲基或烷氧基甲基者為佳。 A crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group, for example, an amine-based resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, or a hydrazine Resin, acetylene urea-formaldehyde resin, succinimide-formaldehyde resin, ethylene urea-formaldehyde resin, and the like. Specifically, a melamine derivative in which a hydrogen atom of an amine group is substituted with a methylol group and/or an alkoxymethyl group, benzindene Derivatives, or acetylene urea or the like can be used. The melamine derivative or benzopyrene The derivative may exist as a dimer or a trimer. These are equivalent to one three The ring is preferably one having an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups.

該些三聚氰胺衍生物或苯併呱衍生物之例如，市售品之每一個三環平均被3.7個甲氧基甲基所取代之MX-750、每一個三環平均被5.8個甲氧基甲基所取代之MW-30(以上、三和化學公司製)，或SIMEL 300、301、303、350、370、771、325、327、703、712等之甲氧基甲基化三聚氰胺、SIMEL 235、236、238、212、253、254等之甲氧基甲基化丁氧基甲基化三聚氰胺、SIMEL 506、508等之丁氧基甲基化三聚氰胺、SIMEL 1141等羧基含有甲氧基甲基化異丁氧基甲基化三聚氰胺、SIMEL 1123等甲氧基甲基化乙氧基甲基化苯併呱、SIMEL 1123-10等甲氧基甲基化丁氧基甲基化苯併呱、SIMEL 1128等丁氧基甲基化苯併呱、SIMEL 1125-80等羧基含有甲氧基甲基化乙氧基甲基化苯併呱 (以上、三井氰胺公司製)等。 These melamine derivatives or benzopyrene For example, each of the three derivatives of the commercial product MX-750, each of which is replaced by 3.7 methoxymethyl groups MW-30 (manufactured by the above, Sanwa Chemical Co., Ltd.), or SIMEL 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc., which is replaced by 5.8 methoxymethyl groups on average. Methoxymethylated melamine, SIMEL 235, 236, 238, 212, 253, 254, etc. methoxymethylated butoxymethylated melamine, SIMEL 506, 508, etc. butoxymethylated melamine, SIMEL The carboxyl group such as 1141 contains methoxymethylated isobutoxymethylated melamine, methoxymethylated ethoxymethylated benzopyrene such as SIMEL 1123 , SIMEL 1123-10 and other methoxymethylated butoxymethylated benzopyrene , butoxymethylated benzopyrene such as SIMEL 1128 , SIMEL 1125-80 and other carboxyl groups contain methoxymethylated ethoxymethylated benzopyrene (above, Mitsui Cyanamide Co., Ltd.), etc.

又，乙炔脲之例如，SIMEL 1170等丁氧基甲基化乙炔脲、SIMEL 1172等羥甲基化乙炔脲等、POWERLINK 1174等甲氧基羥甲基化乙炔脲等。 Further, examples of the acetylene urea include butoxymethylated acetylene urea such as SIMEL 1170, methylolated acetylene urea such as SIMEL 1172, and methoxymethylolated acetylene urea such as POWERLINK 1174.

具有羥基或烷氧基之苯或酚性化合物，例如，1,3,5-三(甲氧基甲基)苯、1,2,4-三(異丙氧基甲基)苯、1,4-雙(sec-丁氧基甲基)苯、2,6-二羥基甲基-p-tert-丁基酚等。 a benzene or a phenolic compound having a hydroxyl group or an alkoxy group, for example, 1,3,5-tris(methoxymethyl)benzene, 1,2,4-tris(isopropoxymethyl)benzene, 1, 4-bis(sec-butoxymethyl)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and the like.

更具體而言，可列舉如，國際公開公報WO2011/132751.(2011.10.27公開)之62~66頁所揭示之式[6-1]~[6-48]所表示之交聯性化合物等。 More specifically, a cross-linking compound represented by the formula [6-1] to [6-48] disclosed in pages 62 to 66 of the International Publication WO2011/132751. .

具有聚合性不飽和鍵結之交聯性化合物，例如，分子內具有3個之三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、三(甲基)丙烯醯氧乙氧基三羥甲基丙烷、丙三醇聚縮水甘油醚聚(甲基)丙烯酸酯等之聚合性不飽和基之交聯性化合物；分子內具有2個乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、伸乙基氧化物雙酚A型二(甲基)丙烯酸酯、伸丙基氧化物雙酚型二(甲基)丙烯酸酯、1,6-己烷二醇二(甲基)丙烯酸酯、丙三醇二(甲基)丙烯酸酯、季戊四 醇二(甲基)丙烯酸酯、乙二醇二縮水甘油醚二(甲基)丙烯酸酯、二乙二醇二縮水甘油醚二(甲基)丙烯酸酯、苯二甲酸二縮水甘油酯二(甲基)丙烯酸酯、羥基叔戊酸新戊二醇二(甲基)丙烯酸酯等之聚合性不飽和基之交聯性化合物；分子內具有1個之2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、2-苯氧基-2-羥基丙基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧-2-羥基丙基苯二甲酸酯、3-氯-2-羥基丙基(甲基)丙烯酸酯、丙三醇單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧乙基磷酸酯、N-羥甲基(甲基)丙烯醯胺等聚合性不飽和基之交聯性化合物等。 a crosslinkable compound having a polymerizable unsaturated bond, for example, having three trimethylolpropane tri(meth)acrylates in the molecule, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(methyl) a crosslinkable compound of a polymerizable unsaturated group such as acrylate, tris(meth)acryloyloxyethoxytrimethylolpropane or glycerol polyglycidyl ether poly(meth)acrylate; 2 ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol Di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethyl bisphenol A Di(meth)acrylate, propylated bisphenol type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerol di(meth)acrylate Quarter four Alcohol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(a) a crosslinkable compound of a polymerizable unsaturated group such as acrylate, hydroxy-t-valeric acid neopentyl glycol di(meth)acrylate, or the like; having one 2-hydroxyethyl (meth) acrylate in the molecule , 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene Indole-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2-(methyl) propylene oxime A crosslinkable compound such as ethyl phosphate or a polymerizable unsaturated group such as N-methylol (meth) acrylamide.

此外，亦可使用下述式[7A]所表示之化合物。 Further, a compound represented by the following formula [7A] can also be used.

(式[7A]中，E1為由環己烷環、雙環己烷環、苯環、聯苯基環、聯三苯基環、萘環、茀環、蒽環及菲環所成之群所選出之至少1個之環，E2表示為下述式[7a]及[7b]所成之群所選出之至少1個之基，n表示1~4之整數)。 (In the formula [7A], E 1 is a group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a biphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring, and a phenanthrene ring; At least one selected ring, E 2 represents at least one selected from the group consisting of the following formulas [7a] and [7b], and n represents an integer of 1 to 4).

上述化合物為交聯性化合物之一例示，但並不僅限定於該些內容。 The above compound is exemplified as one of the crosslinkable compounds, but is not limited to these contents.

又，本發明之液晶配向劑所使用之交聯性化合物，可為1種類亦可、2種類以上之組合亦可。 Further, the crosslinkable compound to be used in the liquid crystal alignment agent of the present invention may be one type or a combination of two or more types.

交聯性化合物之含量，相對於全部聚合物成份100質量份，以0.1~150質量份為佳。其中，就可有效進行交聯反應之目的，相對於全部聚合物成份100質量份，以0.1~100質量份為佳。較佳為1~50質量份。 The content of the crosslinkable compound is preferably 0.1 to 150 parts by mass based on 100 parts by mass of the total polymer component. Among them, the purpose of the crosslinking reaction can be effectively carried out, and it is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the total polymer component. It is preferably 1 to 50 parts by mass.

液晶配向劑，於無損本發明效果之範圍，可含有於塗佈液晶配向劑之際可提高液晶配向膜之膜厚均勻性或表面平滑性之化合物。 The liquid crystal alignment agent may contain a compound which can improve the film thickness uniformity or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment agent is applied, without impairing the effects of the present invention.

可提高液晶配向膜之膜厚均勻性或表面平滑性之化合物，例如，氟系界面活性劑、聚矽氧系界面活性劑、非離子系界面活性劑等。 A compound which can improve the film thickness uniformity or surface smoothness of the liquid crystal alignment film, for example, a fluorine-based surfactant, a polyoxyn-based surfactant, a nonionic surfactant, or the like.

更具體而言，可列舉如，例如，F-TOP EF301、EF303、EF352(以上、陶氏化學製品公司製)、美格氟F171、F173、R-30(以上、大日本塗料公司製)、氟拉多FC430、FC431(以上、住友3M公司製)、AsahiGuard AG710、沙氟隆S-382、SC101、SC102、SC103、SC104、SC105、SC106(以上、旭硝子公司製)等。 More specifically, for example, F-TOP EF301, EF303, EF352 (above, manufactured by Dow Chemical Co., Ltd.), Megfried F171, F173, R-30 (above, manufactured by Dainippon Paint Co., Ltd.), Fluordo FC430, FC431 (above, Sumitomo 3M), AsahiGuard AG710, Shaflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).

該些之界面活性劑之使用比例，相對於液晶配向劑所含有的全部聚合物成份100質量份，較佳為0.01~2質量份、更佳為0.01~1質量份。 The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total polymer component contained in the liquid crystal alignment agent.

此外，本發明之液晶配向劑中，可促進液晶配向膜中之電荷移動的促進元件之電荷解離的化合物，例如，可添加國際公開公報WO2011/132751(2011.10.27公 開)之69~73頁所揭示之式[M1]~[M156]所表示之含氮雜環胺化合物。該胺化合物可直接添加於液晶配向劑中，但以使用適當之溶劑稀釋至濃度0.1~10質量%、較佳為1~7質量%之溶液方式添加為佳。該些之溶劑，只要可溶解上述特定聚合物(A)及特定聚合物(B)之溶劑時，並未有特別之限定。 Further, in the liquid crystal alignment agent of the present invention, a compound which promotes charge dissociation of a charge element in a liquid crystal alignment film can be added, for example, International Publication WO2011/132751 (2011.10.27 public) can be added. The nitrogen-containing heterocyclic amine compound represented by the formula [M1] to [M156] disclosed on pages 69 to 73 of the opening. The amine compound may be directly added to the liquid crystal alignment agent, but it is preferably added by a solution diluted to a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass, using a suitable solvent. These solvents are not particularly limited as long as they dissolve the solvent of the specific polymer (A) and the specific polymer (B).

本發明之液晶配向劑中，除上述貧溶劑、交聯性化合物、可提高樹脂被膜或液晶配向膜之膜厚均勻性或表面平滑性之化合物，及促進電荷解離之化合物以外，於無損及本發明之效果的範圍，可添加以改變液晶配向膜之介電係數或導電性等之電氣特性為目的的介電體或導電物質。 In the liquid crystal alignment agent of the present invention, in addition to the above-mentioned poor solvent and crosslinkable compound, a compound which can improve the film thickness uniformity or surface smoothness of the resin film or the liquid crystal alignment film, and a compound which promotes charge dissociation, A dielectric or a conductive material for the purpose of changing the electrical characteristics such as the dielectric constant or the conductivity of the liquid crystal alignment film may be added to the range of the effects of the invention.

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

液晶配向膜為，將前述液晶配向劑塗佈於基板，經乾燥、燒結而得之膜。 The liquid crystal alignment film is a film obtained by applying the liquid crystal alignment agent to a substrate, drying and sintering.

塗佈液晶配向劑之基板，只要為具有高透明性之基板時，並未有特別之限定，除玻璃基板、氮化矽基板以外，亦可使用丙烯酸基板或聚碳酸酯基板等之塑膠基板等。此時，使用形成有為驅動液晶所使用的ITO電極等之基板時，就製程簡易化之觀點，而為較佳。又，反射型之液晶顯示元件，因僅為單側之基板，亦可使用矽晶圓等之不透明物，該情形之電極，亦可使用可反射鋁等光線之材料。 The substrate to which the liquid crystal alignment agent is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to the glass substrate or the tantalum nitride substrate. . In this case, when a substrate on which an ITO electrode or the like for driving a liquid crystal is formed is used, it is preferable from the viewpoint of simplifying the process. Further, since the reflective liquid crystal display element is only a single-sided substrate, an opaque object such as a germanium wafer or the like may be used. In this case, a material that reflects light such as aluminum may be used.

液晶配向劑之塗佈方法，並未有特別之限定，於工業尚而言，一般為使用網版印刷、平版印刷、凸版 (Flexo)印刷、噴墨法等。該其他之塗佈方法，例如，浸漬法、輥塗佈法、縫狀塗佈法、旋轉塗佈器法、噴霧法等，可配合所需之目的使用該些方法。 The coating method of the liquid crystal alignment agent is not particularly limited, and in the industry, generally, screen printing, lithography, letterpress is used. (Flexo) printing, inkjet method, and the like. The other coating methods, for example, a dipping method, a roll coating method, a slit coating method, a spin coater method, a spray method, etc., can be used for the purpose desired.

液晶配向劑塗佈於基板上之後，可經由加熱板、熱循環型烘箱、IR(紅外線)型烘箱等之加熱手段，使溶劑蒸發而形成液晶配向膜。 After the liquid crystal alignment agent is applied onto the substrate, the solvent can be evaporated by a heating means such as a hot plate, a heat cycle type oven, or an IR (infrared) type oven to form a liquid crystal alignment film.

塗佈液晶配向劑後之乾燥、燒結步驟，可選擇任意之溫度與時間。通常，為充分去除所含有的溶劑時，例如於50~120℃下進行1~10分鐘之燒結，其後，於150~300℃下進行5~120分鐘燒結之條件。 The drying and sintering steps after coating the liquid crystal alignment agent may be selected to any temperature and time. Usually, in order to sufficiently remove the solvent contained, for example, sintering is performed at 50 to 120 ° C for 1 to 10 minutes, and thereafter, sintering is carried out at 150 to 300 ° C for 5 to 120 minutes.

燒結後之液晶配向膜的厚度，並未有特別之限定，過薄時將會有降低液晶顯示元件信賴性之情形，一般以5~300nm為佳。其中，又以10~200nm為佳。 The thickness of the liquid crystal alignment film after sintering is not particularly limited. When it is too thin, the reliability of the liquid crystal display element may be lowered, and it is preferably 5 to 300 nm. Among them, 10~200nm is better.

使所得液晶配向膜進行配向處理之方法，例如，前述摩擦處理法、光配向處理法等，又以光配向處理法為佳。 The method of performing the alignment treatment on the obtained liquid crystal alignment film, for example, the above-described rubbing treatment method, optical alignment treatment method, or the like, is preferably a photo-alignment treatment method.

光配向處理法之具體例，可列舉如，使用特定方向偏向之輻射線照射前述液晶配向膜表面，依各種情況之差異，再於150~250℃之溫度進行加熱處理，以賦予液晶配向性(亦稱為液晶配向能力)之方法等。輻射線，可使用具有波長100~800nm的紫外線或可見光線。其中，又以具有波長100~400nm的紫外線為佳，較佳為具有波長200~400nm的紫外線。 Specific examples of the photo-alignment treatment method include, for example, irradiating the surface of the liquid crystal alignment film with a radiation having a specific direction, and depending on various cases, heat treatment at a temperature of 150 to 250 ° C to impart liquid crystal alignment ( Also known as the method of liquid crystal alignment capability). For radiation, ultraviolet or visible light 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 ultraviolet rays having a wavelength of 200 to 400 nm are preferred.

又，就改善液晶配向性之觀點，可將具有液晶配向膜 之基板於50~250℃持續加熱中，照射輻射線亦可。 Moreover, in terms of improving the alignment of the liquid crystal, the liquid crystal alignment film can be provided. The substrate is continuously heated at 50 to 250 ° C, and the radiation may be irradiated.

輻射線之照射量，以1~10,000mJ/cm2為佳。其中，又以100~5,000mJ/cm2為佳。依此方式所製造之液晶配向膜，可以液晶分子向一定方向安定地配向。 The irradiation amount of the radiation is preferably 1 to 10,000 mJ/cm 2 . Among them, it is preferably 100 to 5,000 mJ/cm 2 . The liquid crystal alignment film produced in this manner can stably align liquid crystal molecules in a certain direction.

此外，照射偏光輻射線之液晶配向膜，可使用水或溶劑，進行接觸處理。所使用的溶劑，只要可溶解經輻射線照射而由液晶配向膜所生成之分解物的溶劑時，則未有特別限定之內容。具體例如，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、丁基溶纖劑(cellosolve)、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、乙酸環己酯等。其中，就廣用性或溶劑安全性之觀點，以水、2-丙醇、1-甲氧基-2-丙醇或乳酸乙酯為佳。較佳為，水、1-甲氧基-2-丙醇或乳酸乙酯。該些之溶劑，可為1種類亦可、2種類以上之組合亦可。 Further, the liquid crystal alignment film which irradiates the polarized radiation can be subjected to a contact treatment using water or a solvent. The solvent to be used is not particularly limited as long as it dissolves a solvent which is irradiated with radiation and is decomposed by the liquid crystal alignment film. Specifically, for example, water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve (cellosolve), ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, and the like. Among them, water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate is preferred from the viewpoint of versatility or solvent safety. Preferred is water, 1-methoxy-2-propanol or ethyl lactate. These solvents may be one type or a combination of two or more types.

本發明中之接觸處理，例如浸漬處理或噴霧處理(亦稱為SPRAY處理)等。該些之處理中之處理時間，就可有效率地溶解因輻射線而由液晶配向膜生成的分解物之觀點，以10秒~1小時為佳。其中，又以1~30分鐘之浸漬處理為佳。又，前述接觸處理時溶劑之溫度，可為常溫或加溫下亦可，較佳為10~80℃。其中，又以20~50℃為佳。就分解物之溶解性之觀點，必要時可再配合超音波處理等方式進行。 The contact treatment in the present invention, for example, immersion treatment or spray treatment (also referred to as SPRAY treatment) or the like. The treatment time in these treatments can efficiently dissolve the decomposition product generated by the liquid crystal alignment film due to the radiation, and it is preferably from 10 seconds to 1 hour. Among them, it is better to immerse for 1 to 30 minutes. Further, the temperature of the solvent during the contact treatment may be normal temperature or heating, and is preferably 10 to 80 °C. Among them, 20~50 °C is preferred. From the viewpoint of the solubility of the decomposition product, it may be carried out by means of ultrasonic treatment if necessary.

前述接觸處理之後，可使用水、甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮等之低沸點溶劑進行水洗(亦稱為洗滌)或進行液晶配向膜燒結者為佳。此時，可進行洗滌與燒結中之任一者，或進行二者皆可。燒結之溫度，以150~300℃為佳。其中，又以180~250℃為佳。較佳為，200~230℃。又，燒結之時間以10秒~30分鐘為佳。其中，又以1~10分鐘為佳。 After the above-mentioned contact treatment, it is preferred to carry out water washing (also referred to as washing) using a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone or to perform liquid crystal alignment film sintering. At this time, either one of washing and sintering may be performed, or both may be performed. The sintering temperature is preferably 150 to 300 ° C. Among them, 180~250 °C is preferred. Preferably, it is 200 to 230 °C. Further, the sintering time is preferably from 10 seconds to 30 minutes. Among them, it is better to take 1~10 minutes.

本發明之液晶配向膜，適合作為IPS方式或FFS方式等之橫電場方式的液晶顯示元件之液晶配向膜，特別是適合作為FFS方式的液晶顯示元件之液晶配向膜。 The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film of a liquid crystal display element of a horizontal electric field type such as an IPS method or an FFS method, and is particularly suitable as a liquid crystal alignment film of an FFS type liquid crystal display element.

本發明之液晶顯示元件，於製得附有由上述液晶配向劑所得之液晶配向膜之基板後，依已知方法製作液晶晶胞，並使用該液晶晶胞作為元件而得者。 In the liquid crystal display device of the present invention, after a substrate having a liquid crystal alignment film obtained from the liquid crystal alignment agent is obtained, a liquid crystal cell is produced by a known method, and the liquid crystal cell is used as an element.

液晶晶胞之製作方法之一例示，將以被動矩陣結構之液晶顯示元件為例進行說明。又，亦可使用於構成影像顯示的各畫素部份上，設有TFT(Thin Film Transistor)等應答元件的主動矩陣結構之液晶顯示元件亦可。 One of the methods for fabricating a liquid crystal cell is exemplified by a liquid crystal display device having a passive matrix structure. Further, it is also possible to use a liquid crystal display element having an active matrix structure in which a response element such as a TFT (Thin Film Transistor) is provided on each pixel portion constituting the image display.

具體而言，為準備透明之玻璃製基板，於一側之基板上設置共用電極，另一側之基板上設置節段電極。該些之電極，例如，可作為ITO電極，而進行可得到所期待之影像顯示的圖型形成(Patterning)。其次，於各基板上，可設置被覆共用電極與節段電極之絶緣膜。絶緣膜，例如，由溶膠-凝膠法所形成之SiO2-TiO2所形成之膜。其次，依前述條件，於各基板上形成液晶配向膜，將 一邊之基板與另一邊之基板，以液晶配向膜面互相為對向之方式重合，周邊使用密封劑接著。密封劑中，就控制基板間隙之觀點，以混入間隔器者為佳。又，於未設置密封劑之面內部份，也以散佈基板間隙控制用之間隔器為佳。密封劑之一部份，以設置有可由外部填充液晶之開口部者為佳。 Specifically, in order to prepare a transparent glass substrate, a common electrode is provided on one of the substrates, and a segment electrode is provided on the other substrate. These electrodes can be used, for example, as ITO electrodes to perform patterning in which desired image display can be obtained. Next, an insulating film covering the common electrode and the segment electrode may be provided on each of the substrates. The insulating film is, for example, a film formed of SiO 2 -TiO 2 formed by a sol-gel method. Next, according to the above conditions, a liquid crystal alignment film is formed on each of the substrates, and the substrate on one side and the substrate on the other side are superposed on each other so that the liquid crystal alignment film faces are opposed to each other, and a sealing agent is used in the periphery. In the sealant, it is preferable to mix the spacers from the viewpoint of controlling the gap of the substrate. Further, it is preferable to use a spacer for controlling the gap of the substrate in the inner portion of the surface on which the sealant is not provided. It is preferable that one part of the sealant is provided with an opening portion through which the liquid crystal can be externally filled.

其後，通過設於密封劑中之開口部，將液晶材料注入由2片基板與密封劑所包圍之空間內。其次，使用接著劑密封此開口部。注入方法，可使用真空注入法亦可，於大氣中利用毛細管現象之方法亦可。 Thereafter, the liquid crystal material is injected into the space surrounded by the two substrates and the sealant through the opening provided in the sealant. Next, the opening is sealed with an adhesive. The injection method may be a vacuum injection method or a capillary phenomenon in the atmosphere.

液晶材料，可使用正型液晶材料或負型液晶材料中之任一種。隨後，進行偏光板之設置。具體而言，以於與2片基板之液晶層為相反側之面貼合一對偏光板者為佳。 As the liquid crystal material, either a positive liquid crystal material or a negative liquid crystal material can be used. Subsequently, the setting of the polarizing plate is performed. Specifically, it is preferable that a pair of polarizing plates are bonded to the surface opposite to the liquid crystal layer of the two substrates.

使用本發明之液晶配向劑時，可製得可抑制因交流驅動所造成之殘像，且，可兼具密封劑及底層基板之密著性的液晶配向膜。特別是，對於照射偏光輻射線之光配向處理法用的液晶配向膜為有用者。 When the liquid crystal alignment agent of the present invention is used, a liquid crystal alignment film which can suppress the afterimage caused by the AC drive and which has both the sealant and the adhesion of the underlying substrate can be obtained. In particular, it is useful for a liquid crystal alignment film for a photo-alignment treatment method that irradiates polarized radiation.

[實施例] [Examples]

以下將列舉實施例，對本發明作更具體之說明，但本發明並不僅限定於該些內容。又，以下所使用的化合物之簡稱，及各特性之測定方法，係如以下所示。 The present invention will be more specifically described by the following examples, but the invention is not limited thereto. Further, the abbreviations of the compounds used below and the methods for measuring the respective properties are as follows.

GBL：γ-丁基內酯 GBL: γ-butyl lactone

BCS：丁基溶纖劑(cellosolve) BCS: butyl cellosolve (cellosolve)

DA-A：下述式(DA-A)所示 DA-A: as shown in the following formula (DA-A)

DA-1：下述式(DA-1)所示 DA-1: shown by the following formula (DA-1)

DA-2：下述式(DA-2)所示 DA-2: as shown in the following formula (DA-2)

DA-3：下述式(DA-3)所示 DA-3: as shown in the following formula (DA-3)

DA-4：下述式(DA-4)所示 DA-4: shown by the following formula (DA-4)

DE-1：下述式(DE-1)所示 DE-1: as shown by the following formula (DE-1)

DAH-1：下述式(DAH-1)所示 DAH-1: as shown by the following formula (DAH-1)

DAH-2：下述式(DAH-2)所示 DAH-2: shown by the following formula (DAH-2)

添加劑A：N-α-(9-茀基甲氧基羰基)-N-τ-t-丁氧基羰基-L-組胺酸 Additive A: N-α-(9-fluorenylmethoxycarbonyl)-N-τ-t-butoxycarbonyl-L-histamine

[1H NMR] [ 1 H NMR]

裝置：傅立葉變換型超導核磁共振裝置(FT-NMR)INOVA-400(Varian製)400MHz Device: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (made by Varian) 400 MHz

溶劑：重氫化二甲基亞碸(DMSO-d6)) Solvent: heavy hydrogenated dimethyl hydrazine (DMSO-d 6 ))

標準物質：四甲基矽烷(TMS) Reference material: tetramethyl decane (TMS)

計算次數：8，或，32 Number of calculations: 8, or 32

[13C{1H}NMR] [ 13 C{ 1 H}NMR]

裝置：傅立葉變換型超導核磁共振裝置(FT-NMR)INOVA-400(Varian製)100MHz Device: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (made by Varian) 100 MHz

溶劑：重氫化二甲基亞碸(DMSO-d6) Solvent: Hydrogenated dimethyl hydrazine (DMSO-d 6 )

標準物質：四甲基矽烷(TMS) Reference material: tetramethyl decane (TMS)

計算次數：256 Number of calculations: 256

[融點測定(DSC)] [melting point measurement (DSC)]

裝置：差示型掃瞄熱量測定裝置DSC1STARe系統(Mettler Toledo製) Device: Differential Scanning Heat Measuring Device DSC1STARe System (Mettler Toledo)

盤：密閉型Au盤 Disk: Closed Au disk

昇溫速度：10℃/min Heating rate: 10 ° C / min

融點：分析最低溫時之吸熱波峰溫度 Melting point: analysis of the endothermic peak temperature at the lowest temperature

[黏度] [viscosity]

聚醯胺酸酯及聚醯胺酸溶液之黏度，為使用E型黏度計TVE-22H(東機產業公司製)，樣品量1.1mL、錐型旋轉器TE-1(1°34’、R24)、溫度25℃下測定者。 The viscosity of the polyamidomate and the polyaminic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample volume of 1.1 mL, and a cone-shaped rotator TE-1 (1°34', R24). ), measured at a temperature of 25 ° C.

[分子量] [molecular weight]

聚醯胺酸酯之分子量為使用GPC(常溫凝膠滲透色層分析儀)裝置予以測定，以聚乙二醇，及聚伸乙基氧化物換算值算出數平均分子量(Mn)與重量平均分子量(Mw)。 The molecular weight of the polyglycolate is determined by a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight (Mn) and the weight average molecular weight are calculated in terms of polyethylene glycol and polyethylene oxide. (Mw).

GPC裝置：Shodex公司製(GPC-101) GPC device: manufactured by Shodex (GPC-101)

管柱：Shodex公司製(KD803、KD805之直列) Pipe column: made by Shodex company (inline of KD803, KD805)

管柱溫度：50℃ Column temperature: 50 ° C

溶離液：N,N-二甲基甲醯胺(添加劑為使用溴化鋰-水和物(LiBr．H2O)為30mmol/L(公升)、磷酸．無水結晶(o-磷酸)為30mmol/L、四氫呋喃(THF)為10ml/L Dissolution: N,N-dimethylformamide (additive is lithium bromide-water (LiBr.H 2 O) is 30 mmol/L (liter), phosphoric acid. anhydrous crystal (o-phosphoric acid) is 30 mmol/L , tetrahydrofuran (THF) is 10ml / L

流速：1.0ml/分 Flow rate: 1.0ml/min

製作檢量線用之標準樣品：東曹公司製TSK標準聚伸乙基氧化物(重量平均分子量(Mw)約900,000、150,000、100,000，及30,000)，及，PolymerLaboratory公司製 聚乙二醇(波峰頂端分子量(Mp)約 12,000、4,000，及1,000)。測定中，為避免波峰重疊，則將900,000、100,000、12,000、1,000等4種類混合所得之樣品，及150,000、30,000、4,000等3種類混合所得之樣品等2種樣品分別進行。 Standard sample for the production of calibration lines: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (Polymer) manufactured by Polymer Laboratory The top molecular weight (Mp) is about 12,000, 4,000, and 1,000). In the measurement, in order to avoid overlapping of the peaks, two samples of a mixture of four types of 900,000, 100,000, 12,000, and 1,000, and a sample obtained by mixing three types of 150,000, 30,000, and 4,000 are separately performed.

[醯亞胺化率之測定] [Determination of sulfhydrylation rate]

合成例中之聚醯亞胺的醯亞胺化率為依以下方式測定者。將聚醯亞胺粉末20mg加入NMR樣品管(NMR標準採樣管， 5(草野科學製))中，添加重氫化二甲基亞碸(DMSO-d6，0.05質量%TMS(四甲基矽烷)混合品)(0.53ml)，施加超音波使其完全溶解。將此溶液於NMR測定機(JNW-ECA500)(日本電子數據製)中測定500MHz之質子NMR。醯亞胺化率，為由醯亞胺化前後未產生變化的結構所產生之質子作為基準質子予以決定，使用此質子之波峰計算值，與9.5ppm~10.0ppm附近出現之由醯胺酸的NH基產生之質子波峰計算值，依以下式所求得者。 The oxime imidization ratio of the polyimine in the synthesis example was measured in the following manner. 20 mg of polyimine powder was added to the NMR sample tube (NMR standard sampling tube, 5 (manufactured by Kusano Scientific)), a solution of dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane)) (0.53 ml) was added, and ultrasonic waves were applied thereto to completely dissolve. This solution was measured for proton NMR at 500 MHz in an NMR measuring machine (JNW-ECA500) (manufactured by J. Am.). The imidization rate of ruthenium is determined by using protons generated by structures that have not changed before and after imidization as a reference proton. The calculated peak value of this proton is used, and the proline is present near 9.5 ppm to 10.0 ppm. The calculated value of the proton peak generated by the NH group is obtained by the following formula.

醯亞胺化率(%)=(1-α．x/y)×100 醯 imidization rate (%) = (1-α.x/y) × 100

上述式中，x為由醯胺酸的NH基產生之質子波峰計算值、y為基準質子之波峰計算值、α為聚醯胺酸(醯亞胺化率為0%)之情形中，相對於1個醯胺酸之NH基質子，基準質子之個數比例。 In the above formula, x is a calculated value of a proton peak derived from an NH group of a proline, y is a calculated peak of a reference proton, and α is a polylysine (a sulfhydrylation ratio of 0%), and is relatively The ratio of the number of reference protons to the NH proton of one proline.

[噴墨印刷] [Inkjet printing]

實施例中所記載之噴墨印刷，為依下述所示裝置、條件進行。裝置名：噴墨印刷之微細圖型塗佈裝置(日立Plant Technologies公司製、HIS-200-1H) The inkjet printing described in the examples was carried out in accordance with the apparatus and conditions shown below. Device name: Fine-pattern coating device for inkjet printing (HITA-200-1H, manufactured by Hitachi Plant Technologies)

塗佈基板：100×100mmITO基板 Coated substrate: 100×100mm ITO substrate

塗佈面積：72×80mm Coating area: 72 × 80mm

塗佈條件：分解能力15μm、平台速度40mm/sec、周波數2000Hz、脈幅9.6μsec、液量42pl、間距寬60μm、間距長141μm、施加電壓：15V、噴嘴縫隙0.5mm Coating conditions: decomposition ability 15 μm, platform speed 40 mm/sec, cycle number 2000 Hz, pulse width 9.6 μsec, liquid amount 42 pl, pitch width 60 μm, pitch length 141 μm, applied voltage: 15 V, nozzle slit 0.5 mm

[液晶晶胞之製作] [Production of liquid crystal cell]

製作具備有FFS(Fringe Field Switching)模式液晶顯示元件之構成的液晶晶胞。首先準備附有電極之基板。基板為大小30mm×50mm、厚度0.7mm之玻璃基板。基板上，第1層為構成對向電極，形成具備有黏稠狀之圖型的ITO電極。第1層之對向電極上，則形成有以CVD法成膜之SiN(氮化矽)膜作為第2層。第2層之SiN膜的膜厚為500nm，具有作為層間絶緣膜之機能。第2層目之SiN膜上，則配置有ITO膜經圖型形成(Patterning)所形成之櫛齒狀之畫素電極作為第3層，而形成第1畫素及第2畫素等2個畫素。各畫素之尺寸為，縱10mm、橫約5mm。此時，第1層之對向電極與第3層之畫素電極之間，則經由第2層之SiN膜的作用而對電形成絶緣。 A liquid crystal cell having a structure of an FFS (Fringe Field Switching) mode liquid crystal display element was produced. First, prepare a substrate with an electrode attached. The substrate was a glass substrate having a size of 30 mm × 50 mm and a thickness of 0.7 mm. On the substrate, the first layer is a counter electrode, and an ITO electrode having a viscous pattern is formed. On the counter electrode of the first layer, a SiN (tantalum 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 has a function as an interlayer insulating film. On the SiN film of the second layer, a dentate-shaped pixel electrode formed by patterning of an ITO film is disposed as a third layer, and two first pixels and a second pixel are formed. Picture. The size of each pixel is 10 mm in length and 5 mm in width. At this time, between the counter electrode of the first layer and the pixel electrode of the third layer, electricity is electrically insulated by the action of the SiN film of the second layer.

第3層之畫素電極，具有多數配列之中央部份為彎曲之「ㄑ」字形狀之電極要素之結構的櫛齒狀之形 狀。各電極要素之短邊方向之寬度為3μm，電極要素間之間隔為6μm。形成各畫素的畫素電極，因具有多數配列之中央部份為彎曲之「ㄑ」字形狀之電極要素的結構，故各畫素的形狀並非長方形，而與電極要素相同般，具備中央部份為彎曲的近似粗體「ㄑ」字的形狀。因此，各畫素以該中央的彎曲部份作為界線分割為上下，而具有彎曲部份之上側的第1區域，與下側的第2區域。 The third layer of the pixel electrode has a structure in which the central portion of the majority of the columns is in the shape of a curved "ㄑ"-shaped electrode element. shape. The width of each electrode element in the short-side direction was 3 μm, and the interval between the electrode elements was 6 μm. Since the pixel electrodes forming the respective pixels have a structure in which the central portion of the majority of the columns is a curved "ㄑ"-shaped electrode element, the shape of each pixel is not a rectangle, and the central portion is the same as the electrode element. The part is a curved shape of the approximate bold "ㄑ". Therefore, each pixel is divided into upper and lower sides by the curved portion of the center as a boundary, and has a first region on the upper side of the curved portion and a second region on the lower side.

各畫素之第1區域與第2區域進行比較時，為構成該些畫素電極的電極要素之形成方向為互相相異。即，於後述液晶配向膜之摩擦方向作為基準之情形，畫素之第1區域中，畫素電極的電極要素為形成+10°之角度(順時鐘方向)，畫素之第2區域中，畫素電極的電極要素則形成-10°之角度(順時鐘方向)。即，具有各畫素之第1區域與第2區域中，經於畫素電極與對向電極之間施加電壓所引起的液晶於基板面內之回轉動作(橫向電場效應(In-Plane．Switching))之方向為互相相反之方向的構成內容。 When the first region and the second region of each pixel are compared, the direction in which the electrode elements constituting the pixel electrodes are formed is different from each other. In other words, in the first region of the pixel, the electrode element of the pixel electrode forms an angle of +10° (clockwise direction) in the first region of the pixel, and in the second region of the pixel, The electrode elements of the pixel electrode form an angle of -10° (clockwise direction). In other words, in the first region and the second region having the respective pixels, the liquid crystal is rotated in the plane of the substrate by applying a voltage between the pixel electrode and the counter electrode (transverse electric field effect (In-Plane. Switching) The direction of the )) is the composition of the opposite direction.

其次，將所得之液晶配向劑使用1.0μm的過濾器過濾之後，使用旋轉塗佈方式塗佈於所準備的附有上述電極之基板與裏面形成ITO膜的具有高度4μm的柱狀間隔器之玻璃基板上。於80℃之加熱板上乾燥5分鐘後，使用230℃的熱風循環式烘箱進行20分鐘之燒結，形成膜厚100nm的塗膜。對此塗膜面施以摩擦或偏光紫外線照射等配向處理後，製得附有液晶配向膜之基板。將 上述2片基板作為一組，於基板上印刷密封劑，將另一片基板，以面向液晶配向膜面之配向方向為0°之方式貼合後，使密封劑硬化而製得空晶胞。使用減壓注入法對此空晶胞注入液晶MLC-2041(莫克股份有限公司製)，將注入口密封，而製得FFS驅動液晶晶胞。其後，將所得液晶晶胞於110℃下加熱1小時，放置一晚後供各評估使用。 Next, the obtained liquid crystal alignment agent was filtered using a 1.0 μm filter, and then coated on the prepared substrate with the above electrode and the ITO film having a columnar spacer having a height of 4 μm by spin coating. On the substrate. After drying on a hot plate at 80 ° C for 5 minutes, it was sintered in a hot air circulating oven at 230 ° C for 20 minutes to form a coating film having a film thickness of 100 nm. After the coating film surface is subjected to an alignment treatment such as rubbing or polarized ultraviolet irradiation, a substrate having a liquid crystal alignment film is obtained. will The two substrates are printed as a group, and the sealing agent is printed on the substrate, and the other substrate is bonded to the liquid crystal alignment film surface at an orientation of 0°, and then the sealing agent is cured to obtain an empty cell. This empty cell was injected into the liquid crystal MLC-2041 (manufactured by Mok Co., Ltd.) by a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 110 ° C for 1 hour, and left for one night for evaluation.

[長期交流驅動所造成之殘像評估] [Residual image evaluation caused by long-term AC drive]

準備與上述殘像評估所使用的液晶晶胞具有同樣結構的液晶晶胞。 A liquid crystal cell having the same structure as that of the liquid crystal cell used in the above-described afterimage evaluation was prepared.

使用此液晶晶胞，於60℃之恆溫環境下，施加周波數60Hz之±5V交流電壓120小時。其後，使液晶晶胞之畫素電極與對向電極之間形成短路之狀態下，於室溫下放置一日。 Using this liquid crystal cell, an AC voltage of ±5 V with a frequency of 60 Hz was applied for 120 hours under a constant temperature environment of 60 °C. Thereafter, in a state where a short circuit between the pixel electrode of the liquid crystal cell and the counter electrode is formed, it is left at room temperature for one day.

放置後，將液晶晶胞與偏光軸為垂直交錯方式設置於所配置的2片偏光板之間，於無施加電壓之狀態下將背光源點燈，將液晶晶胞的配置角度調整至透過光線的亮度達最小程度。隨後，算出液晶晶胞由第1畫素的第2區域的最暗之角度迴轉至第1區域的最暗之角度為止的回轉角度作為△。第2畫素也相同般，使第2區域與第1區域相比較，算出同樣的角度△。隨後，算出第1畫素與第2畫素之角度△值的平均值作為液晶晶胞的角度△，交流驅動殘影△未達0.3則標記為「良好」，其以上則標記為「不良」。 After being placed, the liquid crystal cell and the polarizing axis are vertically interleaved between the two polarizing plates disposed, and the backlight is turned on without applying a voltage, and the arrangement angle of the liquid crystal cell is adjusted to transmit light. The brightness is minimal. Subsequently, the rotation angle at which the liquid crystal cell is rotated from the darkest angle of the second region of the first pixel to the darkest angle of the first region is calculated as Δ. Similarly to the second pixel, the second region is compared with the first region, and the same angle Δ is calculated. Then, 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, and the AC drive residual image Δ is not marked as 0.3, which is marked as “good”, and the above is marked as “bad”. .

[因交流驅動的非對稱化所造成之電荷蓄積值評估] [Evaluation of charge accumulation value due to asymmetry of AC drive]

將所製作之液晶晶胞與偏光軸為垂直交錯方式設置於所配置的2片偏光板之間，於無施加電壓之狀態下將LED背光源點燈後放置，調整液晶晶胞的配置角度以使透過光之亮度達最小之程度。 The liquid crystal cell and the polarizing axis are arranged in a vertical interlacing manner between the two polarizing plates arranged, and the LED backlight is turned on after no voltage is applied, and the arrangement angle of the liquid crystal cell is adjusted. The brightness of the transmitted light is minimized.

其次，於對此液晶晶胞施加周波數30Hz的交流電壓中，測定其V-T曲線(電壓-透過率曲線)，算出相對透過率達50%時之交流電壓作為驅動電壓。 Next, a V-T curve (voltage-transmittance curve) was measured by applying an AC voltage having a cycle number of 30 Hz to the liquid crystal cell, and an AC voltage at a relative transmittance of 50% was calculated as a driving voltage.

以使LED光不會照射到液晶晶胞之方式進行遮光。再對液晶晶胞施加30分鐘的周波數1kHz、20mV之矩形波。 The light is blocked so that the LED light does not illuminate the liquid crystal cell. Further, a rectangular wave having a cycle number of 1 kHz and 20 mV was applied to the liquid crystal cell for 30 minutes.

其後，與LED點燈同時，進行相對透過率達50%之交流驅動，測定點燈後即時的V-F(電壓-閃爍曲線)曲線，算出可消除因交流驅動的非對稱化所造成之電荷蓄積的平版電壓值。測定其後每一分鐘的最小平版電壓值變化量，算出點燈後即時至30分鐘為止變化之際的最大電壓值。此時，以將最大平版電壓之變化量超過20mV的情形定義為「不良」之方式進行評估。又最大平版電壓的變化量未超過20mV之情形中，則以定義為「良好」之方式進行評估。 Thereafter, at the same time as the LED lighting, an AC drive with a relative transmittance of 50% is performed, and an instantaneous VF (voltage-blinking curve) curve after lighting is measured, and the charge accumulation due to the asymmetry of the AC drive can be eliminated. The lithographic voltage value. The amount of change in the minimum lithographic voltage value per minute after the measurement was measured, and the maximum voltage value at the time of the change immediately after the lighting up to 30 minutes was calculated. At this time, the evaluation was made by defining the case where the amount of change in the maximum lithographic voltage exceeds 20 mV as "poor". In the case where the amount of change in the maximum lithographic voltage does not exceed 20 mV, the evaluation is performed in a manner defined as "good".

[電荷緩和特性] [Charge mitigation characteristics]

將上述液晶晶胞放置於光源上，於45℃之溫度下測 定V-T特性(電壓-透過率特性)後，測定施加±1.5V/60Hz之矩形波狀態下之液晶晶胞的透過率(Ta)。其後，於45℃之溫度下施加±1.5V/60Hz之矩形波10分鐘之後，將直流2V重疊後，驅動120分鐘。切斷直流電壓，再分別測定僅使用±1.5V/60Hz之矩形波驅動0分鐘、5分鐘、10分鐘，及20分鐘時的液晶晶胞之透過率(Tb)，再由各時間之透過率(Tb)與初期透過率(Ta)之差(△T)算出殘留於液晶顯示元件內之電壓所生成的透過率之差。 The liquid crystal cell is placed on a light source and measured at a temperature of 45 ° C After the V-T characteristic (voltage-transmittance characteristic) was determined, the transmittance (Ta) of the liquid crystal cell in a rectangular wave state of ±1.5 V/60 Hz was measured. Thereafter, a rectangular wave of ±1.5 V/60 Hz was applied at a temperature of 45 ° C for 10 minutes, and then DC 2 V was superposed and then driven for 120 minutes. The DC voltage was cut off, and the transmittance (Tb) of the liquid crystal cell at 0 minute, 5 minutes, 10 minutes, and 20 minutes was measured using a rectangular wave of ±1.5 V/60 Hz, respectively, and the transmittance of each time was measured. The difference between the transmittance (Tb) and the initial transmittance (Ta) (ΔT) is the difference between the transmittances generated by the voltage remaining in the liquid crystal display element.

(合成例1) (Synthesis Example 1) 芳香族二胺化合物(DA-A)：N-tert-丁氧基羰基-N-(2-(4-胺基苯基)乙基)-N-(4-胺基苄基)胺之合成 Synthesis of Aromatic Diamine Compound (DA-A): N-tert-Butoxycarbonyl-N-(2-(4-Aminophenyl)ethyl)-N-(4-Aminobenzyl) Amine

依以下所示3步驟之過程合成芳香族二胺化合物(DA-A)。又，芳香族二胺化合物(DA-A)為相當於上述特定二胺化合物(2)。 The aromatic diamine compound (DA-A) was synthesized by the procedure of the three steps shown below. Further, the aromatic diamine compound (DA-A) corresponds to the above specific diamine compound (2).

第1步驟：N-(2-(4-硝基苯基)乙基)-N-(4-硝基苄基)胺(DA-A-1)之合成 Step 1: Synthesis of N-(2-(4-nitrophenyl)ethyl)-N-(4-nitrobenzyl)amine (DA-A-1)

使2-(4-硝基苯基)乙基胺鹽酸鹽(50.0g，247mmol)溶解於水(300g)及DMF(50.0g)中，加入碳酸 鈉(78.4g，740mmol)，將4-硝基苄基溴化物(53.3g，247mmol)之DMF溶液(200g)於25℃下以1小時時間滴入。滴入中，追加DMF/水=1/1(w/w、100g)，以消除析出物所造成之攪拌不良狀態。於該狀態下，於室溫下攪拌20小時，此外，於40℃下攪拌4小時，使用HPLC(高速液體色層分析儀)確認原料消失。其後，將反應液放冷至室溫，將析出物過濾，分別使用水(150g)2次、2-丙醇(50.0g)2次洗淨，於50℃下減壓乾燥結果，製得N-2-(4-硝基苯基)乙基-N-(4-硝基苄基)胺(白色固體、產量：73g、產率：99%)。 2-(4-Nitrophenyl)ethylamine hydrochloride (50.0 g, 247 mmol) was dissolved in water (300 g) and DMF (50.0 g). Sodium (78.4 g, 740 mmol), a solution of 4-nitrobenzyl bromide (53.3 g, 247 mmol) in DMF (200 g) was added dropwise at 25 ° C for one hour. During the dropwise addition, DMF/water = 1/1 (w/w, 100 g) was added to eliminate the state of agitation caused by the precipitate. In this state, the mixture was stirred at room temperature for 20 hours, and further stirred at 40 ° C for 4 hours, and the disappearance of the starting material was confirmed by HPLC (High Speed Liquid Chromatography Analyzer). Then, the reaction liquid was allowed to cool to room temperature, and the precipitate was filtered, and washed with water (150 g) twice, 2-propanol (50.0 g) twice, and dried under reduced pressure at 50 ° C to obtain a product. N-2-(4-Nitrophenyl)ethyl-N-(4-nitrobenzyl)amine (white solid, yield: 73 g, yield: 99%).

1H NMR(DMSO-d6)：δ 8.18(d,J=8.8Hz,2H,C6H4),8.15(d,J=8.8Hz,2H,C6H4),7.59,(d,J=8.8Hz,2H,C6H4),7.52(d,J=8.8Hz,2H,C6H4),3.87(s,2H,CH2),2.91(t,J=7.0Hz,2H,CH2),2.80(t,J=7.0Hz,2H,CH2),2.46(s,1H,NH)。13C{1H}NMR(DMSO-d6)：δ 149.8,149.5,146.6,146.3,130.3,129.2,123.7,123.6,52.4,50.0,36.0(each s)。 1 H NMR (DMSO-d 6 ): δ 8.18 (d, J = 8.8 Hz, 2H, C 6 H 4 ), 8.15 (d, J = 8.8 Hz, 2H, C 6 H 4 ), 7.59, (d, J = 8.8 Hz, 2H, C 6 H 4 ), 7.52 (d, J = 8.8 Hz, 2H, C 6 H 4 ), 3.87 (s, 2H, CH 2 ), 2.91 (t, J = 7.0 Hz, 2H , CH 2 ), 2.80 (t, J = 7.0 Hz, 2H, CH 2 ), 2.46 (s, 1H, NH). 13 C{ 1 H} NMR (DMSO-d 6 ): δ 149.8, 149.5, 146.6, 146.3, 130.3, 129.2, 123.7, 123.6, 52.4, 50.0, 36.0 (each s).

融點(DSC)：123℃ Melting point (DSC): 123 ° C

第2步驟：N-tert-丁氧基羰基-N-(2-(4-硝基苯基)乙基)-N-(4-硝基苄基)胺(DA-A-2)之合成 Step 2: Synthesis of N-tert-butoxycarbonyl-N-(2-(4-nitrophenyl)ethyl)-N-(4-nitrobenzyl)amine (DA-A-2)

使N-2-(4-硝基苯基)乙基-N-4-硝基苄基胺(73g，0.24mol)溶解於DMF(371g)中，於2~8℃下以10分鐘滴入二碳酸二tert-丁基(54g，0.24mol)。其後，於20℃下攪拌4小時，使用HPL確認原料消失。隨後，將DMF減壓餾除，反應液中加入乙酸乙酯(371g)，以水(371g)洗淨3次。其後，有機相於減壓下濃縮，得橙色油(粗產量：96g，粗產率：97%)。此粗產物使用矽凝膠管柱色層分析儀(己烷/乙酸乙酯=7/3(v/v，Rf=0.3)精製後得黃色油。(粗產量：82.0g、粗產率：82.8%(2步驟))。於此黃色油中加入甲醇(118g)，於50℃下溶解之後，於攪拌中使其冷卻，於0~5℃下攪拌30分鐘後，經過濾、乾燥後，得N-tert-丁氧基羰基-N-2-(4-硝基苯基)乙基-N-4-硝基苄基胺(白色粉末，產量：74.5g，產率：78%(2步驟))。 N-2-(4-Nitrophenyl)ethyl-N-4-nitrobenzylamine (73 g, 0.24 mol) was dissolved in DMF (371 g), and dropped at 2-8 ° C for 10 minutes. Ditert-butyl dicarbonate (54 g, 0.24 mol). Thereafter, the mixture was stirred at 20 ° C for 4 hours, and the disappearance of the starting material was confirmed using HPL. Subsequently, DMF was distilled off under reduced pressure, and ethyl acetate (371 g) was added to the mixture, and the mixture was washed three times with water (371 g). Thereafter, the organic phase was concentrated under reduced pressure to give an orange oil (yield: yield: 96 g, crude yield: 97%). The crude product was purified using a hexane gel column chromatography (hexane/ethyl acetate=7/3 (v/v, Rf=0.3) to give a yellow oil. (crude yield: 82.0 g, crude yield: 82.8% (2 steps)). To the yellow oil, methanol (118 g) was added, and after dissolving at 50 ° C, it was cooled with stirring, stirred at 0 to 5 ° C for 30 minutes, filtered, dried, N-tert-butoxycarbonyl-N-2-(4-nitrophenyl)ethyl-N-4-nitrobenzylamine (white powder, yield: 74.5 g, yield: 78% (2) step)).

1H NMR(DMSO-d6)：δ 8.22(d,J=8.4Hz,2H,C6H4),8.18-8.16(br,2H,C6H4),7.51(d,J=8.4Hz,2H,C6H4),7.48(br,2H,C6H4),4.57-4.54(br,2H,CH2),3.55-3.49(br,2H,CH2),2.97(br,2H,CH2),1.36-1.32(br,9H,tert-Bu)。13C{1H}NMR(DMSO-d6)：δ 155.2,154.8,147.9,147.5,147.1,147.0,146.5,130.6,128.7,128.4,124.0,123.8,79.7,50.3,49.2,48.4,34.3,34.0,28.2(each s)。 1 H NMR (DMSO-d 6 ): δ 8.22 (d, J = 8.4 Hz, 2H, C 6 H 4 ), 8.18-8.16 (br, 2H, C 6 H 4 ), 7.51 (d, J = 8.4 Hz) , 2H, C 6 H 4 ), 7.48 (br, 2H, C 6 H 4 ), 4.57-4.54 (br, 2H, CH 2 ), 3.55-3.49 (br, 2H, CH 2 ), 2.97 (br, 2H) , CH 2 ), 1.36-1.32 (br, 9H, tert-Bu). 13 C{ 1 H} NMR (DMSO-d 6 ): δ 155.2, 154.8, 147.9, 147.5, 147.1, 147.0, 146.5, 130.6, 128.7, 128.4, 124.0, 123.8, 79.7, 50.3, 49.2, 48.4, 34.3, 34.0 , 28.2 (each s).

融點(DSC)：77℃ Melting point (DSC): 77 ° C

第3步驟：N-tert-丁氧基羰基-N-(2-(4-胺基苯基)乙基)-N-(4-胺基苄基)胺(DA-A)之合成 Step 3: Synthesis of N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine (DA-A)

使N-tert-丁氧基羰基-N-2-(4-硝基苯基)乙基-N-4-硝基苄基胺(74g，0.18mol)溶解於四氫呋喃(370g)中，加入3質量%鉑-碳(7.4g)，氫氣雰圍下，於室溫下攪拌72小時。使用HPLC確認原料之消失，以過濾方式去除觸媒，將濾液濃縮、乾燥後，得薄黃色油之DA-A之粗產物(粗產量：66g、粗產率：105%)。使其於80℃下溶解於甲苯(198g)後，於2℃下攪拌1小時，使結晶析出。將析出之固體過濾、乾燥後，得DA-A(白色粉末、產量：56g、產率：90%)。 N-tert-butoxycarbonyl-N-2-(4-nitrophenyl)ethyl-N-4-nitrobenzylamine (74 g, 0.18 mol) was dissolved in tetrahydrofuran (370 g), and added 3 Mass % platinum-carbon (7.4 g) was stirred at room temperature for 72 hours under a hydrogen atmosphere. The disappearance of the starting material was confirmed by HPLC, and the catalyst was removed by filtration. The filtrate was concentrated and dried to give a crude product (yield: 66 g, crude yield: 105%). After dissolving in toluene (198 g) at 80 ° C, the mixture was stirred at 2 ° C for 1 hour to precipitate crystals. The precipitated solid was filtered and dried to give DA-A (white powder, yield: 56 g, yield: 90%).

1H NMR(DMSO-d6)：δ 6.92(d,J=8.0Hz,2H,C6H4),6.84-6.76(br,2H,C6H4),6.54(d,J=8.0Hz,2H,C6H4),6.50(d,J=8.0Hz,2H,C6H4),4.98(s,2H,NH2),4.84(s,2H,NH2),4.16(br,2H,CH2),3.13(br,2H,CH2),2.51(br,2H,CH2),1.41(s,9H,tert-Bu)。13C{1H}NMR(DMSO-d6)：δ 155.4,154.9,148.2,147.2,129.5,129.3,129.1,128.9,126.6,125.7,114.5,114.3,78.9,78.8,50.2,49.2,48.4,33.9,33.3,28.5(each s)。 1 H NMR (DMSO-d 6 ): δ 6.92 (d, J = 8.0 Hz, 2H, C 6 H 4 ), 6.84-6.76 (br, 2H, C 6 H 4 ), 6.54 (d, J = 8.0 Hz) , 2H, C 6 H 4 ), 6.50 (d, J = 8.0 Hz, 2H, C 6 H 4 ), 4.98 (s, 2H, NH 2 ), 4.84 (s, 2H, NH 2 ), 4.16 (br, 2H, CH 2 ), 3.13 (br, 2H, CH 2 ), 2.51 (br, 2H, CH 2 ), 1.41 (s, 9H, tert-Bu). 13 C{ 1 H} NMR (DMSO-d 6 ): δ 155.4, 154.9, 148.2, 147.2, 129.5, 129.3, 129.1, 128.9, 126.6, 125.7, 114.5, 114.3, 78.9, 78.8, 50.2, 49.2, 48.4, 33.9 , 33.3, 28.5 (each s).

融點(DSC)：103℃ Melting point (DSC): 103 ° C

(合成例2) (Synthesis Example 2)

於附有攪拌裝置及氮導入管的3000mL四口燒瓶中，量取1,2-雙(4-胺基苯氧基)乙烷110.47g(452mmol)、DA-2 18.94g(79.8mmol)，加入NMP 1587g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐111.18g(496mmol)，再加入NMP使固體成份濃度達12質量%，於室溫攪拌24小時，得聚醯胺酸(PAA-1)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為183mPa．s。 1 ,2-bis(4-aminophenoxy)ethane 110.47 g (452 mmol) and DA-2 18.94 g (79.8 mmol) were weighed in a 3000 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 1587 g of NMP was added, and it was stirred and dissolved by nitrogen gas continuously. The diamine solution was continuously stirred, and 111.18 g (496 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was added to make the solid concentration of 12 parts. The mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-1). The polyamic acid solution has a viscosity of 183 mPa at a temperature of 25 ° C. s.

(合成例3) (Synthesis Example 3)

於附有攪拌裝置及氮導入管的2000ml四口燒瓶中，量取所得之聚醯胺酸溶液(PAA-1)950g，加入NMP 677.5g後，攪拌30分鐘。於所得之聚醯胺酸溶液中，加入乙酸酐77.10g、吡啶19.92g，於60℃下加熱3小時，進行化學性醯亞胺化。將所得之反應液於攪拌中投入5177g之甲醇中，濾取析出之沈澱物，隨後，使用5177g之甲醇洗淨3次、1726g之甲醇洗淨2次。所得樹脂粉末於60℃下乾燥12小時後，得聚醯亞胺樹脂粉末。 950 g of the obtained polyaminic acid solution (PAA-1) was weighed in a 2000 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, and 677.5 g of NMP was added thereto, followed by stirring for 30 minutes. 77.10 g of acetic anhydride and 19.92 g of pyridine were added to the obtained polyamic acid solution, and the mixture was heated at 60 ° C for 3 hours to carry out chemical hydrazine imidization. The obtained reaction liquid was poured into 5177 g of methanol under stirring, and the deposited precipitate was collected by filtration, and then washed three times with 5177 g of methanol and twice with 1726 g of methanol. The obtained resin powder was dried at 60 ° C for 12 hours to obtain a polyimide pigment powder.

該聚醯亞胺樹脂粉末之醯亞胺化率為74%、分子量為Mn=8755、Mw=19663。 The polyamidene resin powder had a ruthenium iodide ratio of 74%, a molecular weight of Mn = 8755, and Mw = 19663.

於放置有攪拌子之200ml樣品管中，量取所得之聚醯 亞胺樹脂粉末20.34g，加入NMP149.2g，於40℃下攪拌24小時使其溶解，得聚醯亞胺溶液(SPI-1)。 The obtained polythene was weighed in a 200 ml sample tube in which a stir bar was placed. 20.34 g of the imine resin powder was added to 149.2 g of NMP, and the mixture was stirred at 40 ° C for 24 hours to be dissolved to obtain a polyimine solution (SPI-1).

(合成例4) (Synthesis Example 4)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取p-伸苯基二胺2.92g(27.0mmol)及DA-2 0.71g(3.0mmol)，加入NMP 81.76g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐6.46g(28.8mmol)，再加入NMP使該固體成份濃度達10重量%，於室溫下攪拌4小時，得聚醯胺酸(PAA-2)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為230mPa．s。 2. In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.92 g (27.0 mmol) of p-phenylenediamine and 0.71 g (3.0 mmol) of DA-2 were weighed, and 81.76 g of NMP was added thereto, and the mixture was continuously supplied. Stir in nitrogen to dissolve. The diamine solution was continuously stirred, and 6.46 g (28.8 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was added to make the solid concentration reach 10% by weight, stirred at room temperature for 4 hours to obtain a solution of polyamidamine (PAA-2). The polyamic acid solution has a viscosity of 230 mPa at a temperature of 25 ° C. s.

(合成例5) (Synthesis Example 5)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取1,2-雙(4-胺基苯氧基)乙烷2.93g(12.00mmol)、DA-A 4.43g(11.99mmol)，加入NMP 81.98g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐5.35g(23.88mmol)，再加入NMP 9.11g使該固體成份濃度達12質量%，於室溫攪拌24小時，得聚醯胺酸溶液(PAA-3)。該聚醯胺酸溶液於溫度25℃下之黏度為205mPa．s。 1.2 g of 1,2-bis(4-aminophenoxy)ethane (12.00 mmol) and DA-A 4.43 g (11.99 mmol) were placed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 81.98 g of NMP was added, and it was stirred and dissolved by nitrogen gas continuously. The diamine solution was continuously stirred, and 5.35 g (23.88 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and 9.11 g of NMP was added to make the solid component. The concentration was 12% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a polyamidonic acid solution (PAA-3). The polyamic acid solution has a viscosity of 205 mPa at a temperature of 25 ° C. s.

(合成例6) (Synthesis Example 6)

於附有攪拌裝置及氮導入管的100ml四口燒瓶中，量取所得聚醯胺酸溶液(PAA-3)20g，加入NMP 14.29g後，攪拌30分鐘。於所得之聚醯胺酸溶液中，加入乙酸酐1.48g、吡啶0.38g，於60℃下加熱3小時，進行化學性醯亞胺化。所得反應液於攪拌中，投入139ml之甲醇中，濾取析出之沈澱物，隨後，使用139ml之甲醇洗淨3次。所得樹脂粉末於60℃下乾燥12小時後，得聚醯亞胺樹脂粉末(SPI-2)。 20 g of the obtained polyaminic acid solution (PAA-3) was weighed in a 100 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, and 14.29 g of NMP was added thereto, followed by stirring for 30 minutes. To the obtained polyamic acid solution, 1.48 g of acetic anhydride and 0.38 g of pyridine were added, and the mixture was heated at 60 ° C for 3 hours to carry out chemical hydrazine imidization. The obtained reaction liquid was poured into 139 ml of methanol under stirring, and the precipitate was separated by filtration, and then washed three times with 139 ml of methanol. The obtained resin powder was dried at 60 ° C for 12 hours to obtain a polyimide resin powder (SPI-2).

該聚醯亞胺樹脂粉末之醯亞胺化率為75%、分子量為Mn=8156、Mw=17408。 The polyimine resin powder had a ruthenium iodide ratio of 75%, a molecular weight of Mn = 8156, and Mw = 17408.

(合成例7) (Synthesis Example 7)

於附有攪拌裝置之500mL之四口燒瓶中，使其形成氮雰圍環境，加入p-伸苯基二胺2.80g(25.9mmol)，再加入DA-1 1.45g(6.47mmol)後，加入NMP 111g，及作為鹼之吡啶6.18g(78.1mmol)，攪拌使其溶解。其次，此二胺溶液於持續攪拌中，加入DE-1 9.89g(30.4mmol)，於15℃下反應一晚。攪拌一晚後，加入丙烯醯氯0.38g(4.21mmol)，於15℃下反應4小時。所得聚醯胺酸酯之溶液於攪拌中投入1230g之水中，濾取析出之白色沈澱，隨後，使用1230g之IPA洗淨5次，乾燥後得白色之聚醯胺酸酯樹脂粉末10.2g。產率為83.0%。又，此聚醯胺酸酯之分子量為，Mn=20,786、Mw=40,973。 The mixture was placed in a 500 mL four-necked flask equipped with a stirring apparatus to form a nitrogen atmosphere, and 2.80 g (25.9 mmol) of p-phenylenediamine was added thereto, followed by addition of DA-1 1.45 g (6.47 mmol), followed by addition of NMP. 111 g and 6.18 g (78.1 mmol) of pyridine as a base were stirred and dissolved. Next, the diamine solution was added with stirring, and 9.99 g (30.4 mmol) of DE-1 was added thereto, and the mixture was reacted at 15 ° C overnight. After stirring for one night, 0.38 g (4.21 mmol) of acrylonitrile chloride was added, and the mixture was reacted at 15 ° C for 4 hours. The obtained polyphthalate solution was poured into 1230 g of water under stirring, and the precipitated white precipitate was collected by filtration, and then washed with 1230 g of IPA for 5 times, and dried to obtain 10.2 g of a white polyphthalate resin powder. The yield was 83.0%. Further, the molecular weight of the polyglycolate was Mn = 20,786 and Mw = 40,973.

採取所得之聚醯胺酸酯樹脂粉末7.96g置入100mL三角燒瓶中，加入GBL 72.1g，於室溫下攪拌24小時，使其溶解，得聚醯胺酸酯溶液(PAE-1)。 7.96 g of the obtained polyphthalate resin powder was placed in a 100 mL Erlenmeyer flask, and 72.1 g of GBL was added thereto, and the mixture was stirred at room temperature for 24 hours to be dissolved to obtain a polyamidate solution (PAE-1).

(合成例8) (Synthesis Example 8)

於附有攪拌裝置及氮導入管的1000mL四口燒瓶中，量取4,4’-二胺基二苯基胺39.89g(200.2mmol)、3,5-二胺基安息香酸7.60g(49.95mmol)，加入NMP 282g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入1,2,3,4-丁烷四羧酸二酐14.88g(75.10mmol)，再加入NMP使其固體成份濃度達15質量%，於室溫下攪拌2小時。其次，加入NMP 283g，添加DAH-1 50.3g(171.0mmol)，再加入NMP使其固體成份濃度達12質量%，於室溫下攪拌24小時，得聚醯胺酸(PAA-4)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為393mPa．s。 4,4'-diaminodiphenylamine 39.89 g (200.2 mmol) and 3,5-diaminobenzoic acid 7.60 g (49.95) were weighed in a 1000 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. Mold), 282 g of NMP was added, and it was stirred and dissolved in nitrogen gas continuously. The diamine solution was continuously stirred, and 14.88 g (75.10 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added, and NMP was added thereto to have a solid concentration of 15% by mass, and stirred at room temperature. 2 hours. Next, 283 g of NMP was added, 50.3 g (171.0 mmol) of DAH-1 was added, and NMP was added thereto to have a solid concentration of 12% by mass, and stirred at room temperature for 24 hours to obtain a solution of polyamine acid (PAA-4). . The polyamic acid solution has a viscosity of 393 mPa at a temperature of 25 ° C. s.

(合成例9) (Synthesis Example 9)

於附有攪拌裝置及氮導入管的2000mL四口燒瓶中，量取4,4’-二胺基二苯基胺63.76g(320mmol)、3,5-二胺基安息香酸12.17g(79.99mmol)，加入NMP 1094g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-1 112.59g(383mmol)，再加入NMP使其固體成份濃度達12質量%，於室溫下攪拌24小時， 得聚醯胺酸(PAA-5)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為384mPa．s。 4,4'-diaminodiphenylamine 63.76 g (320 mmol) and 3,5-diaminobenzoic acid 12.17 g (79.99 mmol) were weighed in a 2000 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. Then, 1094 g of NMP was added, and it was stirred and dissolved by nitrogen gas continuously. The diamine solution was continuously stirred, and DAH-1 112.59 g (383 mmol) was added, and NMP was added thereto to have a solid concentration of 12% by mass, and the mixture was stirred at room temperature for 24 hours. A solution of polyamic acid (PAA-5) was obtained. The polyamic acid solution has a viscosity of 384 mPa at a temperature of 25 ° C. s.

(合成例10) (Synthesis Example 10)

於附有攪拌裝置及氮導入管的1000mL四口燒瓶中，量取4,4’-二胺基二苯基胺33.48g(168.0mmol)、DA-3 21.48g(71.99mmol)，加入NMP 803.1g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-1 66.73g(226.8mmol)，再加入NMP使其固體成份濃度達12質量%，於室溫下攪拌24小時，得聚醯胺酸(PAA-6)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為380mPa．s。 4,4'-diaminodiphenylamine 33.48 g (168.0 mmol) and DA-3 21.48 g (71.99 mmol) were weighed in a 1000 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and added to NMP 803.1. g, stirring was carried out by continuously feeding nitrogen gas to dissolve. The diamine solution was continuously stirred, and DAH-1 66.73 g (226.8 mmol) was added thereto, and NMP was added thereto to have a solid concentration of 12% by mass, and stirred at room temperature for 24 hours to obtain polyamic acid (PAA-6). ) a solution. The polyamic acid solution has a viscosity of 380 mPa at a temperature of 25 ° C. s.

(合成例11) (Synthesis Example 11)

於附有攪拌裝置及氮導入管的200mL四口燒瓶中，量取4,4’-二胺基二苯基胺4.44g(20.82mmol)、3,5-二胺基安息香酸0.79g(5.19mmol)，加入NMP 15.71g、GBL 73.08g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-1 7.39g(25.12mmol)，再加入NMP使其固體成份濃度達12質量%，於室溫下攪拌24小時，得聚醯胺酸(PAA-7)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為530mPa．s。 4,4'-diaminodiphenylamine 4.44 g (20.82 mmol) and 3,5-diaminobenzoic acid 0.79 g (5.19) were weighed in a 200 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. Mold), 15.71 g of NMP and 73.08 g of GBL were added, and the mixture was continuously stirred and supplied with nitrogen to be dissolved. The diamine solution was added to 7.39 g (25.12 mmol) of DAH-1, and NMP was added thereto to have a solid concentration of 12% by mass, and stirred at room temperature for 24 hours to obtain polyamic acid (PAA-7). ) a solution. The polyamic acid solution has a viscosity of 530 mPa at a temperature of 25 ° C. s.

(比較合成例1) (Comparative Synthesis Example 1)

於附有攪拌裝置及氮導入管的2000mL四口燒瓶中，量取DA-3 119.35g(400mmol)，加入NMP 1536g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-1 39.43g(386mmol)，再加入NMP使其固體成份濃度達12質量%，於室溫下攪拌24小時，得聚醯胺酸(PAA-9)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為372mPa．s。 In a 2000 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 119.35 g (400 mmol) of DA-3 was weighed, and 1536 g of NMP was added thereto, and the mixture was continuously stirred with nitrogen to be dissolved. The diamine solution was continuously stirred, and DAH-1 39.43 g (386 mmol) was added thereto, and NMP was added thereto to have a solid concentration of 12% by mass, and stirred at room temperature for 24 hours to obtain polyglycine (PAA-9). Solution. The polyamic acid solution has a viscosity of 372 mPa at a temperature of 25 ° C. s.

(合成例12) (Synthesis Example 12)

於附有攪拌裝置及氮導入管的10L多口燒瓶中，量取1,2-雙(4-胺基苯氧基)乙烷488.58g(2mol)、DA-A 184.69g(0.5mol)，加入NMP 7772.47g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐504.38g(2.25mol)，再加入NMP使固體成份濃度達12質量%，於室溫攪拌24小時，得聚醯胺酸(PAA-10)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為192.6mPa．s。 1,8.58 g (2 mol) of 1,2-bis(4-aminophenoxy)ethane and 184.69 g (0.5 mol) of DA-A were weighed in a 10 L multi-necked flask equipped with a stirring device and a nitrogen introduction tube. NMP 7772.47g was added, and it was stirred and dissolved by continuously supplying nitrogen gas. The diamine solution was continuously stirred, and 504.38 g (2.25 mol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was added thereto to have a solid concentration of 12 The mass% was stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-10). The polyamic acid solution has a viscosity of 192.6 mPa at a temperature of 25 ° C. s.

(合成例13) (Synthesis Example 13)

於附有攪拌裝置及氮導入管的3000ml四口燒瓶中，量取所得之聚醯胺酸溶液(PAA-10)2400g，加入NMP 800g，攪拌30分鐘。於所得之聚醯胺酸溶液中，加入乙酸酐186.20g、吡啶48.1g，於60℃下加熱3小時，進行化學性醯亞胺化。所得反應液於攪拌中投入13.21L之甲 醇中，濾取析出之沈澱物，隨後，使用13.21L之甲醇洗淨3次、4.30L之甲醇洗淨2次。所得樹脂粉末於60℃下乾燥12小時後，得聚醯亞胺樹脂粉末。 2400 g of the obtained polyaminic acid solution (PAA-10) was weighed in a 3000 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, and 800 g of NMP was added thereto, followed by stirring for 30 minutes. To the obtained polyamic acid solution, 186.20 g of acetic anhydride and 48.1 g of pyridine were added, and the mixture was heated at 60 ° C for 3 hours to carry out chemical hydrazine imidization. The obtained reaction solution was charged with 13.21 L of a stirring. In the alcohol, the precipitate which precipitated was collected by filtration, and then washed three times with 13.21 L of methanol and twice with 4.30 L of methanol. The obtained resin powder was dried at 60 ° C for 12 hours to obtain a polyimide pigment powder.

該聚醯亞胺樹脂粉末之醯亞胺化率為74%、分子量為Mn=6737、Mw=14181。 The polyamidene resin powder had a ruthenium iodide ratio of 74%, a molecular weight of Mn = 6737, and Mw = 14181.

於放置有攪拌子之200ml樣品管中，量取所得聚醯亞胺樹脂粉末20.34g，加入NMP 149.2g，於40℃下攪拌24小時使其溶解，得聚醯亞胺溶液(SPI-3)。 In a 200 ml sample tube in which a stirrer was placed, 20.34 g of the obtained polyimine resin powder was weighed, and 149.2 g of NMP was added thereto, and the mixture was stirred at 40 ° C for 24 hours to be dissolved to obtain a polyimine solution (SPI-3). .

(合成例14) (Synthesis Example 14)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取DA-4 0.87g(5.8mmol)及4,4’-二胺基二苯基胺4.62g(23.2mmol)，加入NMP 63.24g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-1 4.27g(14.5mmol)及1,2,3,4-環丁烷四羧酸二酐2.56g(13.05mmol)，再添加NMP使固體成份濃度達12重量%，於室溫下攪拌4小時，得聚醯胺酸(PAA-11)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為593mPa．s。 In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.84 g (5.8 mmol) of DA-4 and 4.62 g (23.2 mmol) of 4,4'-diaminodiphenylamine were weighed and added to NMP 63.24. g, stirring was carried out by continuously feeding nitrogen gas to dissolve. The diamine solution was continuously stirred, and 4.27 g (14.5 mmol) of DAH-1 and 2.56 g (13.05 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride were added, and NMP was added to make a solid concentration. After 12% by weight, it was stirred at room temperature for 4 hours to obtain a solution of polyamic acid (PAA-11). The polyamic acid solution has a viscosity of 593 mPa at a temperature of 25 ° C. s.

(合成例15) (Synthesis Example 15)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取4,4’-二胺基二苯基甲烷1.11g(14.0mmol)及4,4’-二胺基二苯基胺4.46g(22.4mmol)，加入NMP 62.02g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-1 4.12g(14mmol)及1,2,3,4-環丁烷四羧酸二酐2.38g(12.18mmol)，再添加NMP使固體成份濃度達12重量%，於室溫下攪拌4小時，得聚醯胺酸(PAA-12)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為590mPa．s。 4,4'-diaminodiphenylmethane 1.11 g (14.0 mmol) and 4,4'-diaminodiphenylamine 4.46 were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. g (22.4mmol), added to NMP 62.02 g was stirred and dissolved in nitrogen gas continuously. The diamine solution was continuously stirred, and 4.18 g (14 mmol) of DAH-1 and 2.38 g (12.18 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride were added, and NMP was added to make the solid concentration reach 12% by weight, stirred at room temperature for 4 hours to obtain a solution of polyamidamine (PAA-12). The polyamic acid solution has a viscosity of 590 mPa at a temperature of 25 ° C. s.

(合成例16) (Synthesis Example 16)

於附有攪拌裝置及氮導入管的5L多口燒瓶中，量取3,5-二胺基安息香酸31.64g(0.2mol)及4,4’-二胺基二苯基胺165.78g(0.83mol)，加入NMP 1270.36g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-2 95.57g(0.31mol)，再添加NMP使其固體成份濃度達15重量%，於室溫下攪拌4小時。其後添加DAH-1 201.95g(0.69mol)，添加NMP使其固體成份濃度達12重量%，於室溫下攪拌4小時，得聚醯胺酸(PAA-13)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為435mPa．s。 A 3,5-diaminobenzoic acid 31.64 g (0.2 mol) and 4,4'-diaminodiphenylamine 165.78 g (0.83) were weighed in a 5 L multi-necked flask equipped with a stirring device and a nitrogen introduction tube. Mol), 1270.36g of NMP was added, and it was stirred and dissolved by continuously feeding nitrogen gas. The diamine solution was continuously stirred, and 95.57 g (0.31 mol) of DAH-2 was added thereto, and NMP was added thereto to have a solid concentration of 15% by weight, and the mixture was stirred at room temperature for 4 hours. Thereafter, 201.95 g (0.69 mol) of DAH-1 was added, NMP was added thereto to have a solid concentration of 12% by weight, and the mixture was stirred at room temperature for 4 hours to obtain a solution of polyamine acid (PAA-13). The polyamic acid solution has a viscosity of 435 mPa at a temperature of 25 ° C. s.

(合成例17) (Synthesis Example 17)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取4,4’-二胺基二苯基甲烷1.11g(14.0mmol)及4,4’-二胺基二苯基胺4.46g(22.4mmol)，加入NMP 64.41g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶 液於持續攪拌中，加入DAH-1 5.77g(19.6mmol)及1,2,3,4-環丁烷四羧酸二酐1.207g(6.16mmol)，再添加NMP使固體成份濃度達12重量%，於室溫下攪拌4小時，得聚醯胺酸(PAA-14)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為387mPa．s。 4,4'-diaminodiphenylmethane 1.11 g (14.0 mmol) and 4,4'-diaminodiphenylamine 4.46 were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. g (22.4 mmol) was added to 64.41 g of NMP, and it was stirred and dissolved in nitrogen gas continuously. This diamine dissolved The liquid was continuously stirred, and 5.17 g (19.6 mmol) of DAH-1 and 1.207 g (6.16 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride were added, and NMP was added to make the solid concentration of 12 parts by weight. The mixture was stirred at room temperature for 4 hours to obtain a solution of polyamidamine (PAA-14). The polyamic acid solution has a viscosity of 387 mPa at a temperature of 25 ° C. s.

(合成例18) (Synthesis Example 18)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取DA-4 0.84g(5.6mmol)及4,4’-二胺基二苯基胺4.46g(22.4mmol)，加入NMP 63.03g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-1 5.77g(19.6mmol)及1,2,3,4-環丁烷四羧酸二酐1.207g(6.16mmol)，再添加NMP使固體成份濃度達12重量%，於室溫下攪拌4小時，得聚醯胺酸(PAA-15)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為396mPa．s。 In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.84 g (5.6 mmol) of DA-4 and 4.46 g (22.4 mmol) of 4,4'-diaminodiphenylamine were weighed and added to NMP 63.03. g, stirring was carried out by continuously feeding nitrogen gas to dissolve. The diamine solution was continuously stirred, and 5.277 g (19.6 mmol) of DAH-1 and 1.207 g (6.16 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride were added, and NMP was added to make a solid concentration. After 12% by weight, it was stirred at room temperature for 4 hours to obtain a solution of polyamic acid (PAA-15). The polyamic acid solution has a viscosity of 396 mPa at a temperature of 25 ° C. s.

(合成例19) (Synthesis Example 19)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取4,4’-二胺基二苯基甲烷1.11g(14.0mmol)及4,4’-二胺基二苯基胺4.46g(22.4mmol)，加入NMP 67.90g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-1 5.77g(19.6mmol)及DAH-2 1.89g(6.16mmol)，再添加NMP使固體成份濃 度達12重量%，於室溫下攪拌4小時，得聚醯胺酸(PAA-16)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為386.8mPa．s。 4,4'-diaminodiphenylmethane 1.11 g (14.0 mmol) and 4,4'-diaminodiphenylamine 4.46 were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. g (22.4 mmol) was added to 67.90 g of NMP, and it was stirred and dissolved in nitrogen gas continuously. The diamine solution was continuously stirred, and 5.77 g (19.6 mmol) of DAH-1 and 1.89 g (6.16 mmol) of DAH-2 were added, and NMP was added to make the solid component thick. The solution was stirred at room temperature for 4 hours to obtain a solution of polyamic acid (PAA-16). The polyamic acid solution has a viscosity of 386.8 mPa at a temperature of 25 ° C. s.

(合成例20) (Synthesis Example 20)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取DA-4 0.81g(5.4mmol)及4,4’-二胺基二苯基胺4.30g(21.6mmol)，加入NMP 64.14g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-2 1.81g(5.94mmol)及DAH-1 5.56g(18.9mmol)，再添加NMP使固體成份濃度達12重量%，於室溫下攪拌4小時，得聚醯胺酸(PAA-17)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為304.0mPa．s。 In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 0.81 g (5.4 mmol) of DA-4 and 4.30 g (21.6 mmol) of 4,4'-diaminodiphenylamine were weighed and added to NMP 64.14. g, stirring was carried out by continuously feeding nitrogen gas to dissolve. The diamine solution was continuously stirred, and 1.81 g (5.94 mmol) of DAH-2 and 5.56 g (18.9 mmol) of DAH-1 were added, and NMP was added to make a solid concentration of 12% by weight, and the mixture was stirred at room temperature for 4 hours. A solution of polyamic acid (PAA-17) was obtained. The polyamic acid solution has a viscosity of 304.0 mPa at a temperature of 25 ° C. s.

(合成例21) (Synthesis Example 21)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取4,4’-二胺基二苯基胺3.82g(19.2mmol)、3,5-二胺基安息香酸0.73g(4.8mmol)，加入NMP 15.38g、GBL 30.76g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-1 4.51g(15.3mmol)，於室溫下攪拌4小時。再添加1,2,3,4-環丁烷四羧酸二酐1.41g(7.2mmol)，添加GBL使固體成份濃度達12質量%，於室溫下攪拌24小時，得聚醯胺酸(PAA-18)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為308.4mPa．s。 4,4'-diaminodiphenylamine 3.82 g (19.2 mmol) and 3,5-diaminobenzoic acid 0.73 g (4.8 g) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. Mg), 15.38 g of NMP and 30.76 g of GBL were added, and the mixture was continuously stirred and supplied with nitrogen to be dissolved. This diamine solution was added to 4.51 g (15.3 mmol) of DAH-1 under stirring, and the mixture was stirred at room temperature for 4 hours. Further, 1.41 g (7.2 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and GBL was added to have a solid concentration of 12% by mass, and stirred at room temperature for 24 hours to obtain polylysine ( A solution of PAA-18). The polyamic acid solution has a viscosity of 308.4 mPa at a temperature of 25 ° C. s.

(合成例22) (Synthesis Example 22)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取4,4’-二胺基二苯基胺3.82g(19.2mmol)、4,4’-二胺基二苯基甲烷0.95g(4.8mmol)，加入NMP 16.74g、GBL 33.48g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-1 6.63g(22.6mmol)，再添加GBL使固體成份濃度達12質量%，於室溫下攪拌24小時，得聚醯胺酸(PAA-19)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為324.4mPa．s。 4,4'-diaminodiphenylamine 3.82 g (19.2 mmol) and 4,4'-diaminodiphenylmethane 0.95 were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. g (4.8 mmol), 16.74 g of NMP and 33.48 g of GBL were added, and the mixture was continuously stirred in nitrogen gas to be dissolved. The diamine solution was continuously stirred, and 6.36 g (22.6 mmol) of DAH-1 was added thereto, and then GBL was added to adjust the solid content to 12% by mass, and the mixture was stirred at room temperature for 24 hours to obtain polylysine (PAA-19). Solution. The polyamic acid solution has a viscosity of 324.4 mPa at a temperature of 25 ° C. s.

(合成例23) (Synthesis Example 23)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取4,4’-二胺基二苯基胺2.86g(14.4mmol)、3,5-二胺基安息香酸0.73g(4.8mmol)，加入NMP 15.78g、GBL 31.55g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-1 6.63g(22.6mmol)，再添加GBL使固體成份濃度達12質量%，於室溫下攪拌24小時，得聚醯胺酸(PAA-20)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為335.5mPa．s。 4,4'-diaminodiphenylamine 2.86 g (14.4 mmol) and 3,5-diaminobenzoic acid 0.73 g (4.8 g) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. Mg), 15.78 g of NMP and 31.55 g of GBL were added, and the mixture was continuously stirred and supplied with nitrogen to be dissolved. The diamine solution was continuously stirred, and 6.36 g (22.6 mmol) of DAH-1 was added thereto, and then GBL was added to adjust the solid content to 12% by mass, and the mixture was stirred at room temperature for 24 hours to obtain polylysine (PAA-20). Solution. The polyamic acid solution has a viscosity of 335.5 mPa at a temperature of 25 ° C. s.

(合成例24) (Synthesis Example 24)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取4,4’-二胺基二苯基胺3.99g(20.0mmol)、3,5-二胺 基安息香酸0.76g(5.0mmol)，加入NMP 15.45g、GBL 3.86g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入1,2,3,4-丁烷四羧酸二酐2.48g(12.5mmol)，於室溫下攪拌4小時。再添加DAH-1 3.31g(11.25mmol)，添加GBL使固體成份濃度達12質量%，於室溫下攪拌24小時，得聚醯胺酸(PAA-21)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為285.2mPa．s。 4,4'-diaminodiphenylamine 3.99 g (20.0 mmol), 3,5-diamine was weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. 0.76 g (5.0 mmol) of ketone acid was added, and 15.45 g of NMP and 3.86 g of GBL were added, and the mixture was continuously stirred and supplied with nitrogen to be dissolved. The diamine solution was continuously stirred, and 2.48 g (12.5 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added, and the mixture was stirred at room temperature for 4 hours. Further, DAH-1 3.31 g (11.25 mmol) was added, and GBL was added to have a solid concentration of 12% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-21). The polyamic acid solution has a viscosity of 285.2 mPa at a temperature of 25 ° C. s.

(合成例25) (Synthesis Example 25)

於附有攪拌裝置及氮導入管的100mL四口燒瓶中，量取1,2-雙(4-胺基苯氧基)乙烷2.81g(11.5mmol)、DA-A 4.24g(11.5mmol)，加入NMP 64.03g，於持續送入氮氣中進行攪拌使其溶解。此二胺溶液於持續攪拌中，加入DAH-1 1.35g(4.6mmol)，於室溫下攪拌4小時。再加入1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐4.06g(18.1mmol)，加入NMP使固體成份濃度達12質量%，於室溫下攪拌24小時，得聚醯胺酸(PAA-22)之溶液。該聚醯胺酸溶液於溫度25℃下之黏度為132.0mPa．s。 The 1,2-bis(4-aminophenoxy)ethane 2.81 g (11.5 mmol) and DA-A 4.24 g (11.5 mmol) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. NMP 64.03g was added, and it was stirred and dissolved by continuously supplying nitrogen gas. This diamine solution was stirred under stirring, and 1.35 g (4.6 mmol) of DAH-1 was added, and the mixture was stirred at room temperature for 4 hours. Further, 4.06 g (18.1 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was added to have a solid concentration of 12% by mass, and stirred at room temperature. In hours, a solution of polyamine acid (PAA-22) was obtained. The polyamic acid solution has a viscosity of 132.0 mPa at a temperature of 25 ° C. s.

(實施例1) (Example 1)

於置有攪拌子之50mL三角燒瓶中，量取合成例3所得之聚醯亞胺溶液(SPI-1)5.49g、合成例8所得之聚醯胺酸溶液(PAA-4)5.14g，0.3質量%之3-環氧丙氧丙基 甲基二乙氧基矽烷的NMP溶液1.24g，加入NMP 4.14g、BCS 4.02g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-1)。 In a 50 mL Erlenmeyer flask equipped with a stirrer, 5.49 g of the polyimine solution (SPI-1) obtained in Synthesis Example 3 and 5.14 g of a polyaminic acid solution (PAA-4) obtained in Synthesis Example 8 were weighed. % by mass of 3-glycidoxypropyl 1.24 g of a NMP solution of methyldiethoxydecane was added to 4.14 g of NMP and 4.02 g of BCS, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (AL-1).

(實施例2) (Example 2)

於置有攪拌子之50mL三角燒瓶中，量取合成例4所得之聚醯胺酸溶液(PAA-2)5.50g、合成例9所得之聚醯胺酸溶液(PAA-5)4.64g，加入0.3質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液1.10g、NMP 4.76g、BCS 4.01g，及添加劑A 0.17g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-2)。 5.50 g of the polyaminic acid solution (PAA-2) obtained in Synthesis Example 4 and 4.64 g of the polyaminic acid solution (PAA-5) obtained in Synthesis Example 9 were weighed and placed in a 50 mL Erlenmeyer flask equipped with a stirrer. 0.3 mass% 3-glycidoxypropylmethyldiethoxydecane NMP solution 1.10g, NMP 4.76g, BCS 4.01g, and additive A 0.17g, stirred with magnetic stirrer for 30 minutes to obtain liquid crystal alignment agent (AL-2).

(實施例3) (Example 3)

於置有攪拌子之50mL三角燒瓶中，量取合成例3所得之聚醯亞胺溶液(SPI-1)5.64g、合成例10所得之聚醯胺酸溶液(PAA-6)5.14g，加入0.3質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液1.24g、NMP 3.98g、BCS 4.02g，及添加劑A 0.19g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-3)。 5.64 g of the polyimine solution (SPI-1) obtained in Synthesis Example 3 and 5.14 g of the polyaminic acid solution (PAA-6) obtained in Synthesis Example 10 were weighed and placed in a 50 mL Erlenmeyer flask equipped with a stirrer. 1.2 mass% of 0.3 mass% 3-glycidoxypropylmethyldiethoxydecane NMP solution, NMP 3.98 g, BCS 4.02 g, and additive A 0.19 g, stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (AL-3).

(實施例4) (Example 4)

於置有攪拌子之200mL三角燒瓶中，量取合成例6所得之聚醯亞胺溶液(SPI-2)5.50g、合成例9所得之聚醯胺酸溶液(PAA-5)5.21g，加入0.3質量%3-環氧丙氧 丙基甲基二乙氧基矽烷之NMP溶液1.24g、NMP 4.04g、BCS 4.02g，及添加劑A 0.19g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-4)。 In a 200 mL Erlenmeyer flask equipped with a stirrer, 5.50 g of the polyimine solution (SPI-2) obtained in Synthesis Example 6 and 5.21 g of the polyamidic acid solution (PAA-5) obtained in Synthesis Example 9 were weighed and added. 0.3% by mass of 3-glycidoxy 1.24 g of a NMP solution of propylmethyldiethoxydecane, 4.04 g of NMP, 4.02 g of BCS, and 0.19 g of an additive A were stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (AL-4).

(實施例5) (Example 5)

於置有攪拌子之200mL三角燒瓶中，量取合成例7所得之聚醯胺酸酯溶液(PAE-1)12.40g、合成例11所得之聚醯胺酸溶液(PAA-7)15.5g，加入NMP 4.96g、GBL 47.14g、PB 20.02g，及添加劑A 0.43g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-5)。 In a 200 mL Erlenmeyer flask equipped with a stirrer, 12.40 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 7 and 15.5 g of the polyamidonic acid solution (PAA-7) obtained in Synthesis Example 11 were weighed. 4.96 g of NMP, 47.14 g of GBL, 20.02 g of PB, and 0.43 g of the additive A were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (AL-5).

(比較例1) (Comparative Example 1)

於置有攪拌子之50mL三角燒瓶中，量取合成例3所得之聚醯亞胺溶液(SPI-1)5.44g、比較合成例1所得之聚醯胺酸溶液(PAA-9)5.17g，加入0.3質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液1.24g、NMP 4.15g、BCS 4.02g，及添加劑A 0.19g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(B-1)。 In a 50 mL conical flask equipped with a stirrer, 5.44 g of the polyimine solution (SPI-1) obtained in Synthesis Example 3 and 5.17 g of the polyamidonic acid solution (PAA-9) obtained in Synthesis Example 1 were weighed. Add 1.34 g of NMP solution of 0.3% by mass of 3-glycidoxypropylmethyldiethoxydecane, 4.15 g of NMP, 4.02 g of BCS, and 0.19 g of additive A, and stir for 30 minutes using a magnetic stirrer to obtain liquid crystal alignment. Agent (B-1).

(實施例6) (Example 6)

實施例1所得之液晶配向劑(AL-1)使用1.0μm之過濾器過濾後，使用旋轉塗佈方式塗佈於所準備之附有上述電極之基板與裏面形成ITO膜的具有高度4μm的柱狀間隔器之玻璃基板。於80℃之加熱板上乾燥5分鐘後， 使用230℃的熱風循環式烘箱進行20分鐘之燒結，形成膜厚100nm的塗膜。介由偏光板將消光比26：1之直線偏光的波長254nm之紫外線以0.2J/cm2照射於此塗膜面。將此基板浸漬於25℃之乙基乳酸酯中5分鐘，其次浸漬於25℃之純水1分鐘，於200℃之加熱板上乾燥5分鐘後，製得附有液晶配向膜之基板。將上述2片基板作為一組，於基板上印刷密封劑，將另一片基板，以面向液晶配向膜面之配向方向為0°之方式貼合後，使密封劑硬化而製得空晶胞。使用減壓注入法對此空晶胞注入液晶MLC-2041(莫克股份有限公司製)，將注入口密封，而製得FFS驅動液晶晶胞。其後，將所得液晶晶胞於110℃下加熱1小時，放置一晚。 The liquid crystal alignment agent (AL-1) obtained in Example 1 was filtered using a 1.0 μm filter, and then applied by spin coating to a substrate having the above-mentioned electrode and a ITO film having a height of 4 μm. A glass substrate of a spacer. After drying on a hot plate at 80 ° C for 5 minutes, it was sintered in a hot air circulating oven at 230 ° C for 20 minutes to form a coating film having a film thickness of 100 nm. Ultraviolet rays having a wavelength of 254 nm whose extinction ratio was linearly polarized at 26:1 were irradiated onto the coating film surface at 0.2 J/cm 2 through a polarizing plate. The substrate was immersed in ethyl lactate at 25 ° C for 5 minutes, then immersed in pure water at 25 ° C for 1 minute, and dried on a hot plate at 200 ° C for 5 minutes to obtain a substrate with a liquid crystal alignment film. The two substrates were used as a group, and a sealant was printed on the substrate, and the other substrate was bonded to the liquid crystal alignment film surface at an orientation of 0°, and then the sealant was cured to obtain an empty cell. This empty cell was injected into the liquid crystal MLC-2041 (manufactured by Mok Co., Ltd.) by a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 110 ° C for 1 hour and allowed to stand overnight.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為6.9%、2.0%、1.1%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, the ΔT of the AC drive for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 6.9%, 2.0%, 1.1%, and 0%, respectively. As a result of evaluation of the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under the driving of 30 minutes was 20 mV or less, which was a good result.

(實施例7) (Example 7)

將實施例2所得之液晶配向劑(AL-2)使用1.0μm之過濾器過濾後，使用旋轉塗佈方式塗佈於所準備之附有 上述電極之基板與裏面形成ITO膜的具有高度4μm的柱狀間隔器之玻璃基板。於80℃之加熱板上乾燥5分鐘後，使用230℃的熱風循環式烘箱進行20分鐘之燒結，形成膜厚100nm的塗膜。介由偏光板將消光比26：1之直線偏光的波長254nm之紫外線以0.5J/cm2照射此塗膜面。將此基板使用230℃的熱風循環式烘箱進行20分鐘之燒結，製得附有液晶配向膜之基板。將上述2片基板作為一組，於基板上印刷密封劑，將另一片基板，以面向液晶配向膜面之配向方向為0°之方式貼合後，使密封劑硬化而製得空晶胞。使用減壓注入法對此空晶胞注入液晶MLC-2041(莫克股份有限公司製)，將注入口密封，而製得FFS驅動液晶晶胞。其後，將所得液晶晶胞於110℃下加熱1小時，放置一晚。 The liquid crystal alignment agent (AL-2) obtained in Example 2 was filtered using a 1.0 μm filter, and then applied by spin coating to the substrate on which the electrode was prepared and the ITO film was formed thereon to have a height of 4 μm. A glass substrate for a column spacer. After drying on a hot plate at 80 ° C for 5 minutes, it was sintered in a hot air circulating oven at 230 ° C for 20 minutes to form a coating film having a film thickness of 100 nm. The coating film surface was irradiated with ultraviolet rays having a wavelength of 254 nm whose extinction ratio was linearly polarized by a polarizing plate by a polarizing plate at 0.5 J/cm 2 . The substrate was sintered in a hot air circulating oven at 230 ° C for 20 minutes to obtain a substrate with a liquid crystal alignment film. The two substrates were used as a group, and a sealant was printed on the substrate, and the other substrate was bonded to the liquid crystal alignment film surface at an orientation of 0°, and then the sealant was cured to obtain an empty cell. This empty cell was injected into the liquid crystal MLC-2041 (manufactured by Mok Co., Ltd.) by a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 110 ° C for 1 hour and allowed to stand overnight.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為6.1%、1.9%、0.9%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, ΔT of AC driving for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 6.1%, 1.9%, 0.9%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例8) (Example 8)

除使用實施例3所得之液晶配向劑(AL-3)以外，其 他皆依實施例6相同之方法製作FFS驅動液晶晶胞。 In addition to using the liquid crystal alignment agent (AL-3) obtained in Example 3, He fabricated the FFS-driven liquid crystal cell in the same manner as in Example 6.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為6.7%、0.5%、0.3%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, ΔT of AC driving for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 6.7%, 0.5%, 0.3%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例9) (Example 9)

除使用實施例4所得之液晶配向劑(AL-4)，於照射偏光紫外線後，使用25℃之純水替代乙基乳酸酯進行5分鐘接觸處理以外，其他皆依實施例6相同之方法製作FFS驅動液晶晶胞。 The same method as in Example 6 was carried out except that the liquid crystal alignment agent (AL-4) obtained in Example 4 was used, after irradiating the polarized ultraviolet light, using pure water of 25 ° C instead of ethyl lactate for 5 minutes of contact treatment. Fabrication of the FFS drive liquid crystal cell.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為4.0%、0.9%、0.5%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, ΔT of AC driving for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 4.0%, 0.9%, 0.5%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例10) (Embodiment 10)

使用實施例5所得之液晶配向劑(AL-5)，除使用噴墨印刷塗佈液晶配向劑以外，其他皆依實施例7相同之方法製作FFS驅動液晶晶胞。 Using the liquid crystal alignment agent (AL-5) obtained in Example 5, an FFS-driven liquid crystal cell was produced in the same manner as in Example 7 except that the liquid crystal alignment agent was applied by inkjet printing.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為8.4%、1.4%、0.9%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, the ΔT of the AC drive for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 8.4%, 1.4%, 0.9%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(比較例2) (Comparative Example 2)

除使用比較例1所得之液晶配向劑(B-1)以外，其他皆依實施例6相同之方法製作FFS驅動液晶晶胞。 An FFS-driven liquid crystal cell was produced in the same manner as in Example 6 except that the liquid crystal alignment agent (B-1) obtained in Comparative Example 1 was used.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為9.9%、0.5%、0.2%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以上，為不良之結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, the ΔT of the AC drive for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 9.9%, 0.5%, 0.2%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or more, which was a poor result.

(實施例11) (Example 11)

於置有攪拌子之50mL三角燒瓶中，量取合成例13所得之聚醯亞胺溶液(SPI-3)3.18g、合成例14所得之聚醯胺酸溶液(PAA-11)4.47g，加入1.0質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液0.9g、NMP 1.34g、GBL 5.4g、BCS 3.60g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-6)。 In a 50 mL Erlenmeyer flask equipped with a stirrer, 3.18 g of the polyimine solution (SPI-3) obtained in Synthesis Example 13 and 4.47 g of the polyaminic acid solution (PAA-11) obtained in Synthesis Example 14 were weighed and added. 1.0 mass% 3-glycidoxypropylmethyldiethoxydecane NMP solution 0.9 g, NMP 1.34 g, GBL 5.4 g, BCS 3.60 g, stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (AL) -6).

(實施例12) (Embodiment 12)

於置有攪拌子之50mL三角燒瓶中，量取合成例13所得之聚醯亞胺溶液(SPI-3)3.18g、合成例15所得之聚醯胺酸溶液(PAA-12)4.10g，加入1.0質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液0.9g、NMP 1.46g、GBL 5.4g、BCS 3.60g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-7)。 3.10 g of the polyimine solution (SPI-3) obtained in Synthesis Example 13 and 4.10 g of the polyamidonic acid solution (PAA-12) obtained in Synthesis Example 15 were added to a 50 mL Erlenmeyer flask equipped with a stirrer, and added. 1.0 mass% 3-glycidoxypropylmethyldiethoxydecane NMP solution 0.9 g, NMP 1.46 g, GBL 5.4 g, BCS 3.60 g, stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (AL) -7).

(實施例13) (Example 13)

於置有攪拌子之50mL三角燒瓶中，量取合成例13所得之聚醯亞胺溶液(SPI-3)3.18g、合成例16所得之聚醯胺酸溶液(PAA-13)4.05g，加入1.0質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液0.9g、NMP 150g、GBL 5.4g、BCS 3.6g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-8)。 In a 50 mL conical flask equipped with a stirrer, 3.18 g of the polyimine solution (SPI-3) obtained in Synthesis Example 13 and 4.05 g of the polyamidonic acid solution (PAA-13) obtained in Synthesis Example 16 were weighed and added. 1.0 mass% 3-glycidoxypropylmethyldiethoxydecane NMP solution 0.9 g, NMP 150 g, GBL 5.4 g, BCS 3.6 g, stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (AL- 8).

(實施例14) (Example 14)

於置有攪拌子之50mL三角燒瓶中，量取合成例13所得之聚醯亞胺溶液(SPI-3)3.18g、合成例17所得之聚醯胺酸溶液(PAA-14)3.99g，加入1.0質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液0.9g、NMP 1.56g、GBL 5.40g、BCS 3.60g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-9)。 In a 50 mL Erlenmeyer flask equipped with a stirrer, 3.18 g of the polyimine solution (SPI-3) obtained in Synthesis Example 13 and 3.99 g of the polyaminic acid solution (PAA-14) obtained in Synthesis Example 17 were weighed and added. 1.0 mass% 3-glycidoxypropylmethyldiethoxydecane NMP solution 0.9 g, NMP 1.56 g, GBL 5.40 g, BCS 3.60 g, stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (AL) -9).

(實施例15) (Example 15)

於置有攪拌子之50mL三角燒瓶中，量取合成例13所得之聚醯亞胺溶液(SPI-3)3.18g、合成例18所得之聚醯胺酸溶液(PAA-15)3.89g，加入1.0質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液0.9g、NMP 1.66g、GBL 5.40g、BCS 3.60g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-10)。 In a 50 mL conical flask equipped with a stirrer, 3.18 g of the polyimine solution (SPI-3) obtained in Synthesis Example 13 and 3.89 g of the polyaminic acid solution (PAA-15) obtained in Synthesis Example 18 were weighed and added. 1.0 mass% 3-glycidoxypropylmethyldiethoxydecane NMP solution 0.9 g, NMP 1.66 g, GBL 5.40 g, BCS 3.60 g, stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (AL) -10).

(實施例16) (Embodiment 16)

於置有攪拌子之50mL三角燒瓶中，量取合成例13所得之聚醯亞胺溶液(SPI-3)3.18g、合成例19所得之聚醯胺酸溶液(PAA-16)3.79g，加入1.0質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液0.9g、NMP 1.76g、GBL 5.40g、BCS 3.60g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-11)。 In a 50 mL Erlenmeyer flask equipped with a stirrer, 3.18 g of the polyimine solution (SPI-3) obtained in Synthesis Example 13 and 3.79 g of the polyaminic acid solution (PAA-16) obtained in Synthesis Example 19 were weighed and added. 1.0 mass% 3-glycidoxypropylmethyldiethoxydecane NMP solution 0.9 g, NMP 1.76 g, GBL 5.40 g, BCS 3.60 g, stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (AL) -11).

(實施例17) (Example 17)

於置有攪拌子之50mL三角燒瓶中，量取合成例13所得之聚醯亞胺溶液(SPI-3)3.18g、合成例20所得之聚醯胺酸溶液(PAA-17)3.96g，加入1.0質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液0.9g、NMP 1.58g、GBL 5.40g、BCS 3.60g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-12)。 In a 50 mL Erlenmeyer flask equipped with a stirrer, 3.18 g of the polyimine solution (SPI-3) obtained in Synthesis Example 13 and 3.96 g of the polyaminic acid solution (PAA-17) obtained in Synthesis Example 20 were weighed and added. 1.0 mass% 3-glycidoxypropylmethyldiethoxydecane NMP solution 0.9 g, NMP 1.58 g, GBL 5.40 g, BCS 3.60 g, stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (AL) -12).

(實施例18) (Embodiment 18)

於置有攪拌子之50mL三角燒瓶中，量取合成例7所得之聚醯胺酸酯溶液(PAE-1)4.8g、合成例21所得之聚醯胺酸溶液(PAA-18)6.02g，加入1.0質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液0.9g、NMP 2.83g、GBL 9.74g、BCS 6.00g加、使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-13)。 4.8 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 7 and 6.02 g of the polylysine solution (PAA-18) obtained in Synthesis Example 21 were weighed in a 50 mL Erlenmeyer flask equipped with a stirrer. Add 1.0% by mass of 3-glycidoxypropylmethyldiethoxydecane to NMP solution 0.9g, NMP 2.83g, GBL 9.74g, BCS 6.00g plus The mixture was stirred for 30 minutes using a magnetic stir bar to obtain a liquid crystal alignment agent (AL-13).

(實施例19) (Embodiment 19)

於置有攪拌子之50mL三角燒瓶中，量取合成例7所得之聚醯胺酸酯溶液(PAE-1)4.8g、合成例22所得之聚醯胺酸溶液(PAA-19)6.17g，加入1.0質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液0.9g、NMP 1.91g、GBL 9.62g、BCS 6.00g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-14)。 4.8 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 7 and 6.17 g of the polylysine solution (PAA-19) obtained in Synthesis Example 22 were weighed in a 50 mL Erlenmeyer flask equipped with a stirrer. 0.9 g of NMP solution of 1.0% by mass of 3-glycidoxypropylmethyldiethoxydecane, 1.91 g of NMP, 9.62 g of GBL, and 6.00 g of BCS were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent ( AL-14).

(實施例20) (Embodiment 20)

於置有攪拌子之50mL三角燒瓶中，量取合成例7所得之聚醯胺酸酯溶液(PAE-1)4.8g、合成例23所得之聚醯胺酸溶液(PAA-20)5.99g，加入1.0質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液0.9g、NMP 1.95g、GBL 9.77g、BCS 6.00g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-15)。 4.8 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 7 and 5.99 g of the polylysine solution (PAA-20) obtained in Synthesis Example 23 were weighed in a 50 mL Erlenmeyer flask equipped with a stirrer. 0.9 g of NMP solution of 1.0% by mass of 3-glycidoxypropylmethyldiethoxydecane, 1.95 g of NMP, 9.77 g of GBL, and 6.00 g of BCS were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent ( AL-15).

(實施例21) (Example 21)

於置有攪拌子之50mL三角燒瓶中，量取合成例7所得之聚醯胺酸酯溶液(PAE-1)4.8g、合成例24所得之聚醯胺酸溶液(PAA-21)6.10g，加入1.0質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液0.9g、NMP 1.92g、GBL 9.67g、BCS 6.00g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-16)。 4.8 g of the polyamidate solution (PAE-1) obtained in Synthesis Example 7 and 6.10 g of the polylysine solution (PAA-21) obtained in Synthesis Example 24 were weighed in a 50 mL Erlenmeyer flask equipped with a stirrer. 0.9 g of NMP solution of 1.0% by mass of 3-glycidoxypropylmethyldiethoxydecane, 1.92 g of NMP, 9.67 g of GBL, and 6.00 g of BCS were added, and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent ( AL-16).

(實施例22) (Example 22)

於置有攪拌子之50mL三角燒瓶中，量取合成例25所得之聚醯胺酸溶液(PAA-22)4.8g、合成例9所得之聚醯胺酸溶液(PAA-5)6.09g，加入1.0質量%3-環氧丙氧丙基甲基二乙氧基矽烷之NMP溶液0.9g、NMP 1.96g、GBL 9.77g、BCS 6.00g，使用磁性攪拌子攪拌30分鐘，得液晶配向劑(AL-17)。 4.8 g of the polyaminic acid solution (PAA-22) obtained in Synthesis Example 25 and 6.09 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 9 were weighed and placed in a 50 mL Erlenmeyer flask equipped with a stirrer. 1.0 mass% 3-glycidoxypropylmethyldiethoxydecane NMP solution 0.9 g, NMP 1.96 g, GBL 9.77 g, BCS 6.00 g, stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (AL) -17).

(實施例23) (Example 23)

實施例11所得之液晶配向劑(AL-6)使用1.0μm之過濾器過濾後，使用旋轉塗佈方式塗佈於所準備之附有上述電極之基板與裏面形成ITO膜的具有高度4μm的柱狀間隔器之玻璃基板。於80℃之加熱板上乾燥5分鐘後，使用230℃的熱風循環式烘箱進行20分鐘之燒結，形成膜厚100nm的塗膜。介由偏光板將消光比26：1之直線偏光的波長254nm之紫外線以0.2J/cm2照射此塗膜面。將此基板浸漬於25℃之乙基乳酸酯中5分鐘，其次浸漬 於25℃之純水1分鐘，於200℃之加熱板上乾燥5分鐘後，製得附有液晶配向膜之基板。將上述2片基板作為一組，於基板上印刷密封劑，將另一片基板，以面向液晶配向膜面之配向方向為0°之方式貼合後，使密封劑硬化而製得空晶胞。使用減壓注入法對此空晶胞注入液晶MLC-2041(莫克股份有限公司製)，將注入口密封，而製得FFS驅動液晶晶胞。其後，將所得液晶晶胞於110℃下加熱1小時，放置一晚。 The liquid crystal alignment agent (AL-6) obtained in Example 11 was filtered using a 1.0 μm filter, and then applied to a substrate having the above electrode and a ITO film having a height of 4 μm by spin coating. A glass substrate of a spacer. After drying on a hot plate at 80 ° C for 5 minutes, it was sintered in a hot air circulating oven at 230 ° C for 20 minutes to form a coating film having a film thickness of 100 nm. The coating film surface was irradiated with ultraviolet rays having a wavelength of 254 nm whose extinction ratio was linearly polarized at 26:1 by a polarizing plate at 0.2 J/cm 2 . The substrate was immersed in ethyl lactate at 25 ° C for 5 minutes, then immersed in pure water at 25 ° C for 1 minute, and dried on a hot plate at 200 ° C for 5 minutes to obtain a substrate with a liquid crystal alignment film. The two substrates were used as a group, and a sealant was printed on the substrate, and the other substrate was bonded to the liquid crystal alignment film surface at an orientation of 0°, and then the sealant was cured to obtain an empty cell. This empty cell was injected into the liquid crystal MLC-2041 (manufactured by Mok Co., Ltd.) by a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 110 ° C for 1 hour and allowed to stand overnight.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為4.5%、0.8%、0.4%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, ΔT of AC driving for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 4.5%, 0.8%, 0.4%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例24) (Example 24)

除使用實施例12所得之液晶配向劑(AL-7)以外，其他皆依實施例23相同之方法製作FFS驅動液晶晶胞。 An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (AL-7) obtained in Example 12 was used.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分 鐘之△T，分別為6.8%、1.2%、0.7%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, the AC drive is 0 minutes, 5 minutes, 10 minutes, and 20 minutes. The △T of the bell is 6.8%, 1.2%, 0.7%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例25) (Embodiment 25)

除使用實施例13所得之液晶配向劑(AL-8)以外，其他皆依實施例23相同之方法製作FFS驅動液晶晶胞。 An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (AL-8) obtained in Example 13 was used.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為6.9%、1.2%、0.8%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, ΔT of AC driving for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 6.9%, 1.2%, 0.8%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例26) (Example 26)

除使用實施例14所得之液晶配向劑(AL-9)以外，其他皆依實施例23相同之方法製作FFS驅動液晶晶胞。 An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (AL-9) obtained in Example 14 was used.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分 鐘之△T，分別為6.5%、1.2%、0.6%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, the AC drive is 0 minutes, 5 minutes, 10 minutes, and 20 minutes. The △T of the bell is 6.5%, 1.2%, 0.6%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例27) (Example 27)

除使用實施例15所得之液晶配向劑(AL-10)以外，其他皆依實施例23相同之方法製作FFS驅動液晶晶胞。 An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (AL-10) obtained in Example 15 was used.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result.

於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為5.5%、1.1%、0.7%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the charge relaxation characteristics, ΔT of AC drive for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 5.5%, 1.1%, 0.7%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例28) (Embodiment 28)

除使用實施例16所得之液晶配向劑(AL-11)以外，其他皆依實施例23相同之方法製作FFS驅動液晶晶胞。 An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (AL-11) obtained in Example 16 was used.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分 鐘之△T，分別為7.3%、1.2%、0.6%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, the AC drive is 0 minutes, 5 minutes, 10 minutes, and 20 minutes. The △T of the clock is 7.3%, 1.2%, 0.6%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例29) (Example 29)

除使用實施例17所得之液晶配向劑(AL-12)以外，其他皆依實施例23相同之方法製作FFS驅動液晶晶胞。 An FFS-driven liquid crystal cell was produced in the same manner as in Example 23 except that the liquid crystal alignment agent (AL-12) obtained in Example 17 was used.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為7.8%、1.4%、0.7%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, the ΔT of the AC drive for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 7.8%, 1.4%, 0.7%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例30) (Embodiment 30)

實施例18所得之液晶配向劑(AL-13)使用1.0μm之過濾器過濾後，使用旋轉塗佈方式塗佈於所準備之附有上述電極之基板與裏面形成ITO膜的具有高度4μm的柱狀間隔器之玻璃基板。於80℃之加熱板上乾燥5分鐘後，使用230℃的熱風循環式烘箱進行20分鐘之燒結，形成膜厚100nm的塗膜。介由偏光板將消光比26：1之 直線偏光的波長254nm之紫外線以0.5J/cm2照射此塗膜面。將此基板使用230℃的熱風循環式烘箱進行20分鐘之燒結，製得附有液晶配向膜之基板。將上述2片基板作為一組，於基板上印刷密封劑，將另一片基板，以面向液晶配向膜面之配向方向為0°之方式貼合後，使密封劑硬化而製得空晶胞。使用減壓注入法對此空晶胞注入液晶MLC-2041(莫克股份有限公司製)，將注入口密封，而製得FFS驅動液晶晶胞。其後，將所得液晶晶胞於110℃下加熱1小時，放置一晚。 The liquid crystal alignment agent (AL-13) obtained in Example 18 was filtered using a 1.0 μm filter, and then applied to a substrate having the above electrode and a ITO film having a height of 4 μm by spin coating. A glass substrate of a spacer. After drying on a hot plate at 80 ° C for 5 minutes, it was sintered in a hot air circulating oven at 230 ° C for 20 minutes to form a coating film having a film thickness of 100 nm. The coating film surface was irradiated with ultraviolet rays having a wavelength of 254 nm whose extinction ratio was linearly polarized by a polarizing plate by a polarizing plate at 0.5 J/cm 2 . The substrate was sintered in a hot air circulating oven at 230 ° C for 20 minutes to obtain a substrate with a liquid crystal alignment film. The two substrates were used as a group, and a sealant was printed on the substrate, and the other substrate was bonded to the liquid crystal alignment film surface at an orientation of 0°, and then the sealant was cured to obtain an empty cell. This empty cell was injected into the liquid crystal MLC-2041 (manufactured by Mok Co., Ltd.) by a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 110 ° C for 1 hour and allowed to stand overnight.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為6.5%、0.2%、0.2%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, ΔT of AC driving for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 6.5%, 0.2%, 0.2%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例31) (Example 31)

除使用實施例19所得之液晶配向劑(AL-14)以外，其他皆依實施例30相同之方法製作FFS驅動液晶晶胞。 An FFS-driven liquid crystal cell was produced in the same manner as in Example 30 except that the liquid crystal alignment agent (AL-14) obtained in Example 19 was used.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特 性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為5.9%、0.3%、0.2%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. Evaluating charge mitigation As a result, AC drives 0 minutes, 5 minutes, 10 minutes, and 20 minutes of ΔT, which are 5.9%, 0.3%, 0.2%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例32) (Example 32)

除使用實施例20所得之液晶配向劑(AL-15)以外，其他皆依實施例30相同之方法製作FFS驅動液晶晶胞。 An FFS-driven liquid crystal cell was produced in the same manner as in Example 30 except that the liquid crystal alignment agent (AL-15) obtained in Example 20 was used.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為4.9%、0.6%、0.3%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, ΔT of AC driving for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 4.9%, 0.6%, 0.3%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例33) (Example 33)

除使用實施例21所得之液晶配向劑(AL-16)以外，其他皆依實施例30相同之方法製作FFS驅動液晶晶胞。 An FFS-driven liquid crystal cell was produced in the same manner as in Example 30 except that the liquid crystal alignment agent (AL-16) obtained in Example 21 was used.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特 性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為6.3%、0.3%、0.2%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. Evaluating charge mitigation As a result, the ΔT of the AC drive for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 6.3%, 0.3%, 0.2%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

(實施例34) (Example 34)

實施例22所得之液晶配向劑(AL-17)使用1.0μm之過濾器過濾後，使用旋轉塗佈方式塗佈於所準備之附有上述電極之基板與裏面形成ITO膜的具有高度4μm的柱狀間隔器之玻璃基板。於80℃之加熱板上乾燥5分鐘後，使用230℃的熱風循環式烘箱進行20分鐘之燒結，形成膜厚100nm的塗膜。此塗膜面於使用人造絲布摩擦(滾筒直徑：120mm、滾筒回轉數：1000rpm、移動速度：20mm/sec、壓入長度：0.3mm)之後，於異丙醇與純水之3/7混合溶劑中照射1分鐘超音波後進行洗淨，使用噴氣流去除水滴後，使用230℃的熱風循環式烘箱進行20分鐘之燒結，製得附有液晶配向膜之基板。將上述2片基板作為一組，於基板上印刷密封劑，將另一片基板，以面向液晶配向膜面之配向方向為0°之方式貼合後，使密封劑硬化而製得空晶胞。使用減壓注入法對此空晶胞注入液晶MLC-2041(莫克股份有限公司製)，將注入口密封，而製得FFS驅動液晶晶胞。其後，將所得液晶晶胞於110℃下加熱1小時，放置一晚。 The liquid crystal alignment agent (AL-17) obtained in Example 22 was filtered using a 1.0 μm filter, and then applied by spin coating to a substrate having the above electrode and a ITO film having a height of 4 μm. A glass substrate of a spacer. After drying on a hot plate at 80 ° C for 5 minutes, it was sintered in a hot air circulating oven at 230 ° C for 20 minutes to form a coating film having a film thickness of 100 nm. The film surface was mixed with rayon cloth (roller diameter: 120 mm, number of drum rotations: 1000 rpm, moving speed: 20 mm/sec, press-in length: 0.3 mm), and then mixed with 3/7 of isopropyl alcohol and pure water. After the ultrasonic wave was irradiated for 1 minute in the solvent, it was washed, and the water droplets were removed by a jet stream, and then sintered in a hot air circulating oven at 230 ° C for 20 minutes to obtain a substrate with a liquid crystal alignment film. The two substrates were used as a group, and a sealant was printed on the substrate, and the other substrate was bonded to the liquid crystal alignment film surface at an orientation of 0°, and then the sealant was cured to obtain an empty cell. This empty cell was injected into the liquid crystal MLC-2041 (manufactured by Mok Co., Ltd.) by a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 110 ° C for 1 hour and allowed to stand overnight.

對此FFS驅動液晶晶胞，進行長期交流驅動所造成之殘像評估之結果，得知長期交流驅動後之此液晶晶胞之角度△之值為0.3度以下，為良好結果。於評估電荷緩和特性之結果，交流驅動0分鐘、5分鐘、10分鐘，及20分鐘之△T，分別為4.0%、0.9%、0.5%，及0%。進行因交流驅動的非對稱化所造成之電荷蓄積值評估之結果，得知30分鐘驅動下之最大平版電壓變化量為20mV以下，為良好結果。 As a result of evaluating the afterimage caused by long-term AC driving by the FFS driving liquid crystal cell, it was found that the angle Δ of the liquid crystal cell after long-term AC driving was 0.3 degrees or less, which was a good result. As a result of evaluating the charge relaxation characteristics, ΔT of AC driving for 0 minutes, 5 minutes, 10 minutes, and 20 minutes was 4.0%, 0.9%, 0.5%, and 0%, respectively. As a result of evaluating the charge accumulation value caused by the asymmetry of the AC drive, it was found that the maximum lithographic voltage change amount under driving for 30 minutes was 20 mV or less, which was a good result.

[產業上之可利用性] [Industrial availability]

由本發明之液晶配向劑所得之液晶配向膜，可抑制因交流驅動的非對稱化所造成之電荷蓄積、提早緩和因直流電壓所蓄積之殘留電荷，此外，也可抑制抑制因交流驅動所造成之殘像，而具有優良殘像特性，適用作為IPS驅動方式或FFS驅動方式的液晶顯示元件或液晶電視之液晶配向膜。 The liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can suppress charge accumulation due to asymmetry of AC driving, prematurely alleviate residual charges accumulated by DC voltage, and suppress suppression by AC driving. It has an afterimage and has excellent afterimage characteristics, and is suitable as a liquid crystal display element of an IPS driving method or an FFS driving method or a liquid crystal alignment film of a liquid crystal television.

特別是，本發明之液晶顯示元件，亦適用於大畫面且具有高精細度之液晶電視或中小型之導航系統或智慧型手機等。 In particular, the liquid crystal display element of the present invention is also applicable to a large-screen and high-definition liquid crystal television or a small-sized navigation system or a smart phone.

又，2013年10月23日申請之日本專利申請2013-219840號之說明書、專利申請專利範圍，及摘要等全內容皆於本說明書中引用，而作為本發明之說明書之揭示內容。 The entire contents of the specification, the patent application, and the abstract of Japanese Patent Application No. 2013-219840, filed on Jan.

Claims (20)

一種液晶配向劑，其特徵為，含有下述(A)成份，及(B)成份，(A)成份：選自聚醯亞胺前驅物，及該聚醯亞胺前驅物經醯亞胺化所得之聚醯亞胺之至少1種聚合物，該聚醯亞胺前驅物係使含有具有選自下述式[1b-1]所示結構之至少1種結構之二胺成分，與四羧酸成分聚縮合而得者； (式[1b-1]中，X3及X7各自獨立表示由單鍵、碳數1~10之伸烷基、-O-、-N(R1)-、-CON(R2)-、-N(R3)CO-、-CH2O-、-COO-及-OCO-所選出之至少1種；但，R1、R2及R3各自獨立表示氫原子或碳數1~3之烷基；X4及X6各自獨立表示單鍵或碳數1~10之伸烷基，X5表示單鍵或碳數1~10之伸烷基，Xc表示選自由下述之式[a-1]至[a-6]所成群之至少1種結構，r表示1~4之整數；A3、A4各自獨立表示氫原子、碳數1~10之烷基、碳數1~10之烯基，或碳數1~10之炔基，該些之基可具有取代基) (式[a-2]中，R1表示碳數1~5之烷基)(B)成份：由下述含有式(B-1)之四羧酸二酐的四 羧酸成份，與下述含有式(B-2)之二胺的二胺成份經聚縮合反應所得之聚醯胺酸及該聚醯亞胺前驅物經醯亞胺化所得之聚醯亞胺所成之群所選出之至少1種的聚合物； (式中，Y1為具有由胺基、亞胺基，及含氮雜環所成之群所選出之至少1種類的結構之2價之有機基；B1及B2各自獨立表示氫原子、碳數1~10之烷基、碳數1~10之烯基，或碳數1~10之炔基，該些之基可具有取代基)。 A liquid crystal alignment agent comprising the following (A) component, and (B) component, (A) component: selected from the group consisting of a polyimide precursor, and the polyimide precursor is imidized At least one polymer of the obtained polyimine, the polyimine precursor containing a diamine component having at least one structure selected from the group consisting of the following formula [1b-1], and a tetracarboxylic acid The acid component is obtained by condensation; (In the formula [1b-1], X 3 and X 7 each independently represent a single bond, an alkyl group having 1 to 10 carbon atoms, -O-, -N(R 1 )-, -CON(R 2 )- At least one selected from the group consisting of -N(R 3 )CO-, -CH 2 O-, -COO-, and -OCO-; however, R 1 , R 2 and R 3 each independently represent a hydrogen atom or a carbon number of 1~ 3 alkyl; X 4 and X 6 each independently represent a single bond or a C 1-10 alkyl group, X 5 represents a single bond or a C 1-10 alkyl group, and X c represents a group selected from the group consisting of At least one of the groups of the formulae [a-1] to [a-6], r represents an integer of 1 to 4; and A 3 and A 4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and carbon. An alkenyl group of 1 to 10 or an alkynyl group having 1 to 10 carbon atoms, which may have a substituent) (In the formula [a-2], R 1 represents an alkyl group having 1 to 5 carbon atoms) (B) Component: a tetracarboxylic acid component containing the following tetracarboxylic dianhydride of the formula (B-1), and The polyamine component containing the diamine component of the formula (B-2) is selected from the group consisting of polyglycine obtained by a polycondensation reaction and the polyimine obtained by ruthenium imidization of the polyimide precursor. At least one polymer; (wherein Y 1 is a divalent organic group having at least one type of structure selected from the group consisting of an amine group, an imido group, and a nitrogen-containing heterocyclic ring; and B 1 and B 2 each independently represent a hydrogen atom; And an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, wherein the groups may have a substituent). 如請求項1之液晶配向劑，其中，前述二胺為由下述式[1d-4]及式[1d-5]所成之群所選出之至少1種的二胺； (式[1d-4]、式[1d-5]中，R5~R7各自獨立表示由下述式[a-1]~式[a-6]所成之群所選出之至少1種之結構，A7~A10各自獨立表示氫原子、碳數1~10之烷基、碳數1~10之烯基，或碳數1~10之炔基，該些之基可具有取代基)； (式[a-2]中，R1表示碳數1~5之烷基)。 The liquid crystal alignment agent of claim 1, wherein the diamine is at least one diamine selected from the group consisting of the following formula [1d-4] and the formula [1d-5]; (In the formula [1d-4], the formula [1d-5], R 5 to R 7 each independently represent at least one selected from the group consisting of the following formulas [a-1] to [a-6]. In the structure, A 7 to A 10 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, and these groups may have a substituent. ); (In the formula [a-2], R 1 represents an alkyl group having 1 to 5 carbon atoms). 如請求項1之液晶配向劑，其中，前述(A)成份之聚合物更包含由含有下述式[3-1]所表示之二胺的二胺成份與四羧酸成份經聚縮合而得之聚醯亞胺前驅物及該聚醯亞胺前驅物經醯亞胺化所得之聚醯亞胺所成之群所選出之至少1種； (式[3-1]中，XE表示由下述式[3a-1]~式[3a-10]所成之群所選出之至少1種之結構，A1及A2各自獨立表示氫原子、碳數1~10之烷基、碳數1~10之烯基，或碳數1~10之炔基，該些之基可具有取代基) (式[3a-9]中，n表示1~5之整數)。 The liquid crystal alignment agent of claim 1, wherein the polymer of the component (A) further comprises a polycondensation of a diamine component and a tetracarboxylic acid component containing a diamine represented by the following formula [3-1]. At least one selected from the group consisting of a polyimine precursor and a polyimine imide obtained by hydrazine imidization; (In the formula [3-1], X E represents a structure selected from at least one selected from the group consisting of the following formula [3a-1] to the formula [3a-10], and A 1 and A 2 each independently represent hydrogen. An atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkynyl group having 1 to 10 carbon atoms, which may have a substituent) (in the formula [3a-9], n represents an integer of 1 to 5). 如請求項1~3中任一項之液晶配向劑，其中，前述四羧酸成份為下述式[4]所表示之四羧酸二酐； (Z表示由下述式[4a]~[4q]所成之群所選出之至少1種之結構) (式[4a]中，Z1~Z4各自獨立表示氫原子、甲基、乙基、丙基、氯原子或苯環，式[4g]中，Z5及Z6各自獨立表示氫原子或甲基)。 The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the tetracarboxylic acid component is a tetracarboxylic dianhydride represented by the following formula [4]; (Z represents a structure of at least one selected from the group consisting of the following formulas [4a] to [4q]) (In the formula [4a], Z 1 to Z 4 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, and in the formula [4g], Z 5 and Z 6 each independently represent a hydrogen atom or methyl). 如請求項4之液晶配向劑，其中，前述四羧酸成份為，前述式[4]中之Z為由前述式[4a]、式[4e]~式[4g]、式[4l]、式[4m]或式[4p]所成之群所選出之至少1種的四羧酸化合物。 The liquid crystal alignment agent according to claim 4, wherein the tetracarboxylic acid component is such that Z in the above formula [4] is represented by the above formula [4a], formula [4e] to formula [4g], formula [4l], At least one tetracarboxylic acid compound selected from the group of [4m] or the formula [4p]. 如請求項1~3中任一項之液晶配向劑，其中，前述(A)成份之聚合物中，前述式[1b-1]所示之二胺，於全二胺成份100莫耳%中，為5~30莫耳%。 The liquid crystal alignment agent of any one of the above-mentioned (A) component, wherein the diamine represented by the above formula [1b-1] is 100% by mole of the total diamine component. , for 5~30 mol%. 如請求項1~3中任一項之液晶配向劑，其中，前 述(B)成份中，前述式(B-1)所表示之四羧酸二酐，相對於全四羧酸成份1莫耳，為10~100莫耳%。 The liquid crystal alignment agent according to any one of claims 1 to 3, wherein In the component (B), the tetracarboxylic dianhydride represented by the above formula (B-1) is 10 to 100 mol% based on 1 mol of the total tetracarboxylic acid component. 如請求項1~3中任一項之液晶配向劑，其中，前述(B)成份中，前述式(B-2)之二胺，相對於全二胺成份1莫耳，為10~100莫耳%。 The liquid crystal alignment agent according to any one of claims 1 to 3, wherein, in the component (B), the diamine of the above formula (B-2) is 10 to 100 moles relative to the total diamine component 1 mole. ear%. 如請求項1~3中任一項之液晶配向劑，其中，前述式(B-2)中之Y1為由具有下述式(YD-1)~式(YD-5)所表示之氮原子的2價之有機基所成之群所選出之至少1種； (式(YD-1)中，E1為碳數3~15之含氮原子之雜環，Q1為氫原子，或可具有取代基之素數1~20之烴基；式(YD-2)中，W1為碳數1~10之烴基，E2為具有含氮原子之雜環的碳數3~15之1價之有機基，或被碳數1~6之脂肪族基所取代的二取代胺基；式(YD-3)中，W2為碳數6~15，且具有1~2個苯環之2價之有機基，W3為碳數2~5之伸烷基或伸聯苯基，Q2為氫原子、碳數1~5 之烷基，或苯環；a為0~1之整數；式(YD-4)中，E3為碳數3~15之含氮原子之雜環；式(YD-5)中，E4為碳數3~15之含氮原子之雜環，W5為碳數2~5之伸烷基)。 The liquid crystal alignment agent of any one of the above formula (B-2), wherein Y 1 in the above formula (B-2) is a nitrogen represented by the following formula (YD-1) to formula (YD-5) At least one selected from the group consisting of an atomic divalent organic group; (In the formula (YD-1), E 1 is a heterocyclic ring containing a nitrogen atom having 3 to 15 carbon atoms, Q 1 is a hydrogen atom, or a hydrocarbon group having a prime number of 1 to 20 which may have a substituent; In the above, W 1 is a hydrocarbon group having 1 to 10 carbon atoms, and E 2 is a monovalent organic group having a carbon number of 3 to 15 having a hetero ring containing a nitrogen atom, or is substituted by an aliphatic group having 1 to 6 carbon atoms. a disubstituted amine group; in the formula (YD-3), W 2 is a carbon number of 6 to 15, and has a divalent organic group of 1 to 2 benzene rings, and W 3 is an alkylene group having 2 to 5 carbon atoms. Or a biphenyl group, Q 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a benzene ring; a is an integer of 0 to 1; in the formula (YD-4), E 3 is a carbon number of 3 to 15 a heterocyclic ring containing a nitrogen atom; in the formula (YD-5), E 4 is a heterocyclic ring containing a nitrogen atom having 3 to 15 carbon atoms, and W 5 is an alkylene group having 2 to 5 carbon atoms). 如請求項1~3中任一項之液晶配向劑，其中，前述式(YD-1)、式(YD-2)、式(YD-4)，及式(YD-5)記載之E1、E2、E3，及E4之碳數3~15之含氮原子之雜環，為由吡咯、吡咯、咪唑、吡唑、噁唑、噻唑、哌啶、哌、吡啶、吡、吲哚、苯併咪唑、喹啉，及異喹啉所成之群所選出之至少1種。 The liquid crystal alignment agent according to any one of claims 1 to 3, wherein E 1 described in the above formula (YD-1), formula (YD-2), formula (YD-4), and formula (YD-5) a heterocyclic ring containing a carbon atom of 3 to 15 carbon atoms of E 2 , E 3 , and E 4 , which is pyrrole , pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine Pyridine, pyridyl At least one selected from the group consisting of hydrazine, benzimidazole, quinoline, and isoquinoline. 如請求項1~3中任一項之液晶配向劑，其中，前述式(B-2)之Y1為由具有下述式(YD-6)~式(YD-21)所表示之氮原子的2價之有機基所成之群所選出之至少1種； (式(YD-17)中，h為1~3之整數，式(YD-14)及式(YD-21)中，j為0~3之整數)。 The liquid crystal alignment agent of any one of the above formula (B-2), wherein Y 1 of the above formula (B-2) is a nitrogen atom represented by the following formula (YD-6) to formula (YD-21) At least one selected from the group consisting of two organic groups; (In the formula (YD-17), h is an integer from 1 to 3, and in the formula (YD-14) and the formula (YD-21), j is an integer from 0 to 3). 如請求項11之液晶配向劑，其中，前述式(B-2)之Y1為由具有前述式(YD-14)及式(YD-18)所表示之氮原子的2價之有機基所成之群所選出之至少1種。 The liquid crystal alignment agent of claim 11, wherein Y 1 of the above formula (B-2) is a divalent organic group having a nitrogen atom represented by the above formula (YD-14) and formula (YD-18) At least one selected from the group. 如請求項1~3中任一項之液晶配向劑，其中，前述(B)成份之聚合物，相對於前述(A)成份之聚合物100質量份，為40~250質量份。 The liquid crystal alignment agent according to any one of the above-mentioned items (1), wherein the polymer of the component (B) is 40 to 250 parts by mass based on 100 parts by mass of the polymer of the component (A). 如請求項1~3中任一項之液晶配向劑，其為含有由N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮及γ-丁內酯所成之群所選出之至少1種的溶劑。 The liquid crystal alignment agent according to any one of claims 1 to 3, which comprises a group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone At least one solvent selected. 如請求項1~3中任一項之液晶配向劑，其為含有由1-己醇、環己醇、1,2-乙烷二醇、1,2-丙烷二醇、丙二醇單丁基醚、乙二醇單丁基醚及二丙二醇二甲基醚所成之 群所選出之至少1種的溶劑。 The liquid crystal alignment agent according to any one of claims 1 to 3, which comprises 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether , ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether At least one solvent selected from the group. 如請求項1~3中任一項之液晶配向劑，其為含有由，具有環氧基、異氰酸酯基、環氧丙烷基或環碳酸酯基之交聯性化合物、具有由羥基、羥烷基或低級烷氧基烷基所成之群所選出之至少1種的取代基之交聯性化合物，及具有聚合性不飽和鍵結之交聯性化合物所成之群所選出之至少1種。 The liquid crystal alignment agent according to any one of claims 1 to 3, which is a crosslinkable compound having an epoxy group, an isocyanate group, an oxypropylene group or a cyclic carbonate group, having a hydroxyl group or a hydroxyalkyl group. At least one selected from the group consisting of a crosslinkable compound having at least one substituent selected from the group consisting of a lower alkoxyalkyl group and a crosslinkable compound having a polymerizable unsaturated bond. 一種液晶配向膜，其特徵為，將請求項1~16中任一項之液晶配向劑經塗佈、燒結而製得。 A liquid crystal alignment film obtained by coating and sintering a liquid crystal alignment agent according to any one of claims 1 to 16. 一種液晶配向膜，其特徵為，使用請求項1~16中任一項之液晶配向劑，經噴墨法而製得。 A liquid crystal alignment film obtained by an inkjet method using the liquid crystal alignment agent according to any one of claims 1 to 16. 一種液晶配向膜，其特徵為，使用偏光之輻射線照射於請求項17或18之液晶配向膜上而製得。 A liquid crystal alignment film obtained by irradiating a liquid crystal alignment film of claim 17 or 18 with a radiation of polarized light. 一種液晶顯示元件，其特徵為，具有請求項17~19中任一項之液晶配向膜者。 A liquid crystal display element comprising the liquid crystal alignment film of any one of claims 17 to 19.
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