TW201400549A - Polyimide-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Polyimide-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element Download PDF

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TW201400549A
TW201400549A TW102111536A TW102111536A TW201400549A TW 201400549 A TW201400549 A TW 201400549A TW 102111536 A TW102111536 A TW 102111536A TW 102111536 A TW102111536 A TW 102111536A TW 201400549 A TW201400549 A TW 201400549A
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crystal alignment
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Hiromitsu Matsumoto
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Nissan Chemical Ind Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
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    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—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
    • 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

Provided is a liquid crystal aligning agent that forms a liquid crystal alignment film having good rubbing resistance, good printability even when the imidization rate is high, an excellent voltage retention rate, a high accumulated charge, and the like. This liquid crystal aligning agent is characterized by comprising a soluble polyimide represented by formula (1), and a polyamic acid ester represented by formula (2). (X1 is a tetravalent organic group, Y1 is a divalent organic group, X2 is a tetravalent organic group, Y2 is a divalent organic group, R1 is a C1-5 alkyl group, A1 and A2 each independently are a hydrogen atom, or a C1-10 alkyl group, alkenyl group, or alkynyl group which may optionally have a substituent.)

Description

聚醯亞胺系之液晶配向處理劑、液晶配向膜、及液晶顯示元件 Polyimine-based liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element

本發明係關於一種聚醯亞胺系之液晶配向處理劑、使用有聚醯亞胺系之液晶配向處理劑的液晶配向膜、及液晶顯示元件。 The present invention relates to a polyimine-based liquid crystal alignment treatment agent, a liquid crystal alignment film using a polyimine-based liquid crystal alignment treatment agent, and a liquid crystal display element.

液晶顯示元件，係為利用有作成以於基板上形成有液晶分子的液晶配向膜所挾持之結構，且此液晶分子藉由電壓而進行回應的顯示元件。 The liquid crystal display element is a display element which is formed by a liquid crystal alignment film formed with a liquid crystal molecule formed on a substrate, and which is responsive to a voltage by the liquid crystal molecules.

液晶配向膜係具有將液晶分子的配向方向與預傾角控制成任意狀態之重要的功能。 The liquid crystal alignment film has an important function of controlling the alignment direction and the pretilt angle of the liquid crystal molecules to an arbitrary state.

液晶配向膜，一般而言係對於形成於基板上的聚醯亞胺膜之表面，藉由嫘縈、耐隆布等對其表面施加壓力而進行擦拭、所謂「摩擦處理」所製作。藉由此摩擦處理而決定液晶分子的配向方向。 The liquid crystal alignment film is generally produced by rubbing a surface of a polyimide film formed on a substrate by applying pressure to a surface thereof by using a crucible, a rag, or the like. The alignment direction of the liquid crystal molecules is determined by the rubbing treatment.

將液晶之預傾角加大的手段，已知有於形成有液晶配向膜的聚醯亞胺之結構中導入長鏈之烷基的手段(例如，參照專利文獻1)。 In the means for increasing the pretilt angle of the liquid crystal, a method of introducing a long-chain alkyl group into a structure of a polyimide having a liquid crystal alignment film is known (for example, see Patent Document 1).

使聚醯亞胺膜形成於基板上的手段，有塗佈 聚醯胺酸等之溶液使其在基板上予以醯亞胺化的方法、以及塗佈可溶性聚醯亞胺之溶液的方法。其中，使用可溶性聚醯亞胺之溶液的方法，係即使較為低溫的燒成，也能夠形成作為液晶配向膜時之特性為良好的聚醯亞胺膜，相反地，卻有所形成之膜的強度低，藉由摩擦處理容易引起對膜表面之損傷及膜之剝離的問題。 a means for forming a polyimide film on a substrate A method of imidating a solution of polylysine or the like on a substrate, and a method of coating a solution of soluble polyimine. Among them, a method of using a solution of a soluble polyimine is capable of forming a polyimide film having a good property as a liquid crystal alignment film even when it is fired at a relatively low temperature, and conversely, a film formed. The strength is low, and the problem of damage to the surface of the film and peeling of the film is easily caused by the rubbing treatment.

此外，製作液晶配向膜時將聚合物溶液塗佈於基板的手段，目前，工業上廣泛使用有柔版印刷法。但，醯亞胺化率高的可溶性聚醯亞胺之溶液會引起白化現象等之印刷性不佳，因此，需要將醯亞胺化率低的可溶性聚醯亞胺等混合使用等的功夫(例如，參照專利文獻2)。 Further, a method of applying a polymer solution to a substrate when producing a liquid crystal alignment film is currently widely used in the industry by a flexographic printing method. However, a solution of a soluble polyimine having a high yield of ruthenium has a poor printability such as a whitening phenomenon, and therefore it is necessary to mix and use a soluble polyimine having a low ruthenium amide ratio. For example, refer to Patent Document 2).

進而，若為了賦予液晶較大的預傾角，而將長鏈烷基導入可溶性聚醯亞胺的結構中，則會有該印刷性惡化的傾向。 Further, when a long-chain alkyl group is introduced into the structure of the soluble polyimine in order to impart a large pretilt angle to the liquid crystal, the printability tends to be deteriorated.

對聚合物溶液之基板的印刷性之改善手段，已知有添加丁基賽路蘇等之溶劑的方法(例如，參照專利文獻3)。 A method of adding a solvent such as butyl sarbuta to a substrate for improving the printability of a substrate of a polymer solution is known (for example, see Patent Document 3).

但，一般而言，可溶性聚醯亞胺係相較於聚醯胺酸等溶解性較低，因此無法多量使用丁基賽路蘇等之溶劑。 However, in general, the soluble polyimine-based phase has a lower solubility than poly-lysine, and therefore it is not possible to use a solvent such as butyl sirolimus in a large amount.

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1：日本特開平2-282726號公報 Patent Document 1: Japanese Patent Laid-Open No. Hei 2-282726

專利文獻2：日本特開平9-297312號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. H9-297312

專利文獻3：日本特開平2-037324號公報 Patent Document 3: Japanese Patent Laid-Open No. 2-037324

本發明之目的係提供一種聚醯亞胺系之液晶配向處理劑，其係可得到耐摩擦性良好的液晶配向膜，且即使可溶性聚醯亞胺之醯亞胺化率高，但印刷性仍良好，且含有電壓保持率(VHR)、積蓄電荷(RDC)等之電特性優異的可溶性聚醯亞胺。 An object of the present invention is to provide a polyimine-based liquid crystal alignment treatment agent which can obtain a liquid crystal alignment film having good rubbing resistance, and even if the soluble polyimide pigment has a high imidization ratio, the printability is still It is a soluble polyimine which is excellent in electrical properties such as voltage holding ratio (VHR) and accumulated charge (RDC).

本發明者發現，不損及含有上述可溶性聚醯亞胺的聚醯亞胺系之液晶配向處理劑的特性、電特性，尤其，進行欲改善被膜形成時之印刷特性的研究時，含有具有特定的結構之可溶性聚醯亞胺，並且具有特定的結構之聚醯胺酸酯的液晶配向處理劑係可達成該目的。 The present inventors have found that the properties and electrical properties of the polyimine-based liquid crystal alignment treatment agent containing the above-mentioned soluble polyimine are not impaired, and in particular, when the study is to improve the printing characteristics at the time of film formation, A liquid crystalline alignment treatment agent having a structure of a soluble polyimine and having a specific structure of a polyphthalate can achieve the object.

亦即，含有具有特定的結構之可溶性聚醯亞胺，並且具有特定的結構之聚醯胺酸酯的液晶配向處理劑，係能夠提供一種即使醯胺化率高於塗膜形成時也不會引起白化現象，印刷性良好，且塗膜之耐摩擦性良好的液晶配向膜。此外發現：所得到的液晶配向膜係電特性優異，尤其，於電壓保持率及積蓄電荷(RDC)方面具有前所未有的優異特性。 That is, a liquid crystal alignment treatment agent containing a polyamidimide having a specific structure and having a specific structure of a polyphthalate can provide a film which does not have a higher amidation rate than when a coating film is formed. A liquid crystal alignment film which causes whitening phenomenon, is excellent in printability, and has good abrasion resistance of a coating film. Further, it has been found that the obtained liquid crystal alignment film is excellent in electrical characteristics, and particularly has excellent characteristics in terms of voltage holding ratio and accumulated charge (RDC).

亦即，本發明係基於上述見解而完成者，且具有下述要旨。 That is, the present invention has been completed based on the above findings, and has the following gist.

1.一種液晶配向處理劑，其特徵為含有以下述式(1)所表示的可溶性聚醯亞胺、與以下述式(2)所表示的聚醯胺酸酯。 A liquid crystal alignment treatment agent comprising a soluble polyimine represented by the following formula (1) and a polyphthalate represented by the following formula (2).

(式(1)中，X1為4價之有機基，Y1為2價之有機基；式(2)中，X2為4價之有機基，Y2為2價之有機基，R1為碳數1~5之烷基；A1及A2係各自獨立為氫原子、或可具有取代基之碳數1~10之烷基、烯基或炔基)。 (In the formula (1), X 1 is a tetravalent organic group, Y 1 is a divalent organic group; in the formula (2), X 2 is a tetravalent organic group, and Y 2 is a divalent organic group, R 1 is an alkyl group having 1 to 5 carbon atoms; and each of A 1 and A 2 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an alkynyl group which may have a substituent.

2.如上述1所記載之液晶配向處理劑，其中式(2)中之R1為甲基。 2. The liquid crystal alignment treatment agent according to the above 1, wherein R 1 in the formula (2) is a methyl group.

3.如上述1或2所記載之液晶配向處理劑，其中於式(1)、式(2)中之X1及X2係各自獨立為由以下述式所表示之結構中所選出的至少一種。 3. The liquid crystal alignment treatment agent according to the above 1 or 2, wherein X 1 and X 2 in the formula (1) and the formula (2) are each independently at least selected from the structures represented by the following formulas. One.

4.如上述1~3中任一項所記載之液晶配向處理劑，其中於式(2)中，X2係具有芳香族環之以下的結構。 4. The liquid crystal alignment treatment agent according to any one of the above-mentioned items 1 to 3, wherein, in the formula (2), the X 2 system has a structure of an aromatic ring or less.

5.如上述1~3中任一項所記載之液晶配向處理劑，其中於式(1)中，X1係具有脂肪族結構或脂環式結構。 The liquid crystal alignment treatment agent according to any one of the above-mentioned items 1 to 3, wherein, in the formula (1), the X 1 system has an aliphatic structure or an alicyclic structure.

6.如上述1~5中任一項所記載之液晶配向處理劑，其中前述聚醯胺酸酯的重量平均分子量為5,000~200,000。 The liquid crystal alignment treatment agent according to any one of the above 1 to 5, wherein the polyglycolate has a weight average molecular weight of 5,000 to 200,000.

7.如上述1~6中任一項所記載之液晶配向處理劑， 其中前述可溶性聚醯亞胺係具有醯亞胺化率50%以上，且重量平均分子量為5,000~200,000。 7. The liquid crystal alignment treatment agent according to any one of the above 1 to 6, The soluble polyamidene has a ruthenium iodide ratio of 50% or more and a weight average molecular weight of 5,000 to 200,000.

8.如上述1~7中任一項所記載之液晶配向處理劑，其中前述可溶性聚醯亞胺的含量與前述聚醯胺酸酯的含量之比(可溶性聚醯亞胺的含量/聚醯胺酸酯的含量)係以質量比率計為1/9~9/1。 8. The liquid crystal alignment treatment agent according to any one of the above 1 to 7, wherein the ratio of the content of the soluble polyimine to the content of the polyamidolate (the content of the soluble polyamidene/concentration) The content of the amine ester is 1/9 to 9/1 in terms of a mass ratio.

9.如上述1~8中任一項所記載之液晶配向處理劑，其中含有用以溶解前述可溶性聚醯亞胺與前述聚醯胺酸酯的有機溶劑，且可溶性聚醯亞胺的含量與聚醯胺酸酯之合計量係相對於有機溶劑100質量%為0.5~15質量%。 The liquid crystal alignment treatment agent according to any one of the above 1 to 8, which contains an organic solvent for dissolving the soluble polyimine and the polyamidomate, and the content of the soluble polyimine and The total amount of the polyphthalamide is 0.5 to 15% by mass based on 100% by mass of the organic solvent.

10.如上述9所記載之液晶配向處理劑，其中前述有機溶劑係含有由N-甲基-吡咯啶酮、N-乙基-吡咯啶酮、及γ-丁內酯所成之群中所選出的至少1種。 10. The liquid crystal alignment treatment agent according to the above 9, wherein the organic solvent contains a group of N-methyl-pyrrolidone, N-ethyl-pyrrolidone, and γ-butyrolactone. At least one of the selected ones.

11.如上述1~10中任一項所記載之液晶配向處理劑，其中進一步含有溶劑。 The liquid crystal alignment treatment agent according to any one of the above 1 to 10, further comprising a solvent.

12.如上述11所記載之液晶配向處理劑，其中前述溶劑為丁基賽路蘇。 12. The liquid crystal alignment treatment agent according to the above 11, wherein the solvent is butyl siroli.

13.一種液晶配向膜，其係塗佈如上述1~12中任一項所記載之液晶配向處理劑，並加以燒成所得。 A liquid crystal alignment film obtained by baking the liquid crystal alignment treatment agent according to any one of the above 1 to 12, which is obtained by firing.

14.如上述13所記載之液晶配向膜，其中塗佈前述液晶配向處理劑，並加以燒成所得到的塗膜之厚度為5~300nm。 14. The liquid crystal alignment film according to the above-mentioned item 13, wherein the coating film obtained by applying the liquid crystal alignment agent and baking is 5 to 300 nm in thickness.

15.一種液晶顯示元件，其係具備如上述13或14所 記載之液晶配向膜。 A liquid crystal display element comprising the above 13 or 14 The liquid crystal alignment film is described.

若依據本發明之液晶配向處理劑，則可得到即使可溶性聚醯亞胺之醯亞胺化率高，於塗膜形成時也不會引起白化現象，印刷性仍良好，且塗膜之耐摩擦性良好的液晶配向膜。此外，所得到的液晶配向膜係電特性優異，尤其，於電壓保持率及積蓄電荷(RDC)中具有前所未有的優異特性。 According to the liquid crystal alignment treatment agent of the present invention, even if the soluble polyimide pigment has a high imidization ratio, it does not cause whitening when the coating film is formed, the printability is good, and the coating film is resistant to abrasion. A good liquid crystal alignment film. Further, the obtained liquid crystal alignment film is excellent in electrical characteristics, and particularly has excellent characteristics superior to voltage holding ratio and accumulated charge (RDC).

於本發明中，乃思及藉由使用聚醯胺酸酯，極性或脂溶性會接近可溶性聚醯亞胺，因此不會形成如下所述之2層，即使於與液晶接觸的界面，也會以具有聚醯胺酸酯的濃度存在之故。 In the present invention, by using polyglycolate, the polar or fat solubility is close to the soluble polyimine, so that the two layers described below are not formed, even at the interface with the liquid crystal. It is present in a concentration having a polyphthalate.

另一方面，於取代本發明之液晶配向處理劑所含有的聚醯胺酸酯，而使用有聚醯胺酸的情況中，塗膜形成時之白化現象雖得以改善，但卻得到所得之液晶配向膜於電壓保持率、積蓄電荷(RDC)等特性方面無法得到滿足的結果。 On the other hand, in the case where polyphthalamide is used instead of the polyphthalate contained in the liquid crystal alignment agent of the present invention, the whitening phenomenon at the time of formation of the coating film is improved, but the obtained liquid crystal is obtained. The alignment film is not satisfactory in terms of characteristics such as voltage holding ratio and accumulated charge (RDC).

雖於使用有聚醯胺酸取代聚醯胺酸酯的情況中之造成電特性降低的原因尚未明瞭，但由於在使用有聚醯胺酸的情況中，極性或脂溶性與可溶性聚醯亞胺不同，因此被認為乃起因於成為可溶性聚醯亞胺成分位於液晶配向膜之上層，且聚醯胺酸成分位於下層之二層系者。 Although the reason for the decrease in electrical characteristics in the case of using polylysine instead of polyphthalate is not clear, due to the use of polylysine, polar or fat-soluble and soluble polyimine Differently, it is considered to be caused by the fact that the soluble polyamidene component is located on the upper layer of the liquid crystal alignment film, and the poly-proline component is located in the lower layer of the lower layer.

<可溶性聚醯亞胺> <soluble polyimine>

本發明所使用的可溶性聚醯亞胺係具有以下述之式(1)所表示的結構。 The soluble polyamidene used in the present invention has a structure represented by the following formula (1).

於上述式(1)中，X1為4價之有機基。 In the above formula (1), X 1 is a tetravalent organic group.

若展示X1之較佳的具體例，則可列舉如下所示之X-1~X-46。就單體之取得性的觀點而言，X1係以X-1、X-2、X-3、X-4、X-5、X-6、X-8、X-16、X-19、X-21、X-25、X-26、X-27、X-28或X-32為佳。 If Specific examples of preferred X 1 shows, can be exemplified as follows as shown in X-1 ~ X-46. From the viewpoint of monomer availability, X 1 is X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-19. X-21, X-25, X-26, X-27, X-28 or X-32 are preferred.

其中，X1係具有脂肪族結構或脂環式結構時，由於所得到的液晶配向膜具有高的電壓保持率特性，故為佳。較理想之具有脂肪族結構的X1係以X-1、X-16、X-19為佳，特別是以X-1、X-19為佳。 Among them, when the X 1 system has an aliphatic structure or an alicyclic structure, it is preferred because the obtained liquid crystal alignment film has high voltage holding ratio characteristics. Preferably, the X 1 system having an aliphatic structure is preferably X-1, X-16 or X-19, particularly preferably X-1 or X-19.

此外，於式(1)中，Y1為2價之有機基，並未特別限定。若展示Y1之較佳的具體例，則可列舉下述之Y-1~Y-97。 Further, in the formula (1), Y 1 is a divalent organic group, and is not particularly limited. When a preferred specific example of Y 1 is shown, the following Y-1 to Y-97 can be cited.

其中，Y1係以Y-7、Y-10、Y-11、Y-12、Y-13、Y-21、Y-22、Y-23、Y-25、Y-26、Y-27、Y-41、Y-42、Y-43、Y-44、Y-45、Y-46、Y-48、Y-61、Y-63、Y-64、Y-71、Y-72、Y-73、Y-74、Y-75、Y-98為更佳，以具有此 等結構之二胺化合物為佳。 Among them, Y 1 is Y-7, Y-10, Y-11, Y-12, Y-13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y-45, Y-46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y- 73. Y-74, Y-75, and Y-98 are more preferable, and a diamine compound having such a structure is preferred.

此外，Y1為Y-76、Y-77、Y-78、Y-79、Y-80、Y-81、Y-82、Y-83、Y-84、Y-85、Y-86、Y-87、Y-88、Y-89、Y-90、Y-91、Y-92、Y-93、Y-94、Y-95、Y-96、或Y-97時，係可提高預傾角。 Further, Y 1 is Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y -87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, or Y-97, can improve the pretilt angle .

本發明所使用的可溶性聚醯亞胺，係藉由既知的方法將聚醯亞胺前驅物予以醯亞胺化而得到。聚醯亞 胺前驅物係意味著聚醯胺酸或聚醯胺酸酯。 The soluble polyimine used in the present invention is obtained by imidating a polyimine precursor by a known method. Jujua The amine precursor system means polyamic acid or polyamidomate.

於醯亞胺化中使用聚醯胺酸時係藉由將聚醯胺酸進行脫水閉環，此外，使用聚醯胺酸酯時係藉由將聚醯胺酸進行加熱閉環而製造。 When polylysine is used in the imidization, polylysine is subjected to dehydration ring closure, and polyglycolate is produced by heating and ring-closing polylysine.

其中，於本發明中，由於將聚醯胺酸進行脫水閉環的方法可提高醯亞胺化率，故為更佳。 Among them, in the present invention, the method of dehydrating and ring-closing polylysine can improve the ruthenium iodide ratio, which is more preferable.

本發明之可溶性聚醯亞胺的醯亞胺化率，係可藉由調節醯亞胺化反應中之觸媒量、反應溫度、反應時間等而加以控制。於本發明中，由於亦可使用醯亞胺化率高的聚醯亞胺，因此醯亞胺化率係以50%以上為佳，以70%以上為更佳，以80%以上特別佳。其中，醯亞胺化率係以80~90%為更佳。 The sulfonium imidization ratio of the soluble polyimine of the present invention can be controlled by adjusting the amount of the catalyst in the sulfiliation reaction, the reaction temperature, the reaction time, and the like. In the present invention, since the polyimine having a high yield of ruthenium iodide can also be used, the sulfhydrylation ratio is preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more. Among them, the sulfhydrylation rate is preferably from 80 to 90%.

聚醯胺酸係藉由二胺成分與四羧酸二水物之反應並藉由既知的方法而得到。 Polylysine is obtained by a reaction of a diamine component and a tetracarboxylic acid dihydrate by a known method.

此外，聚醯胺酸酯係依據既知的方法，藉由使二胺成分與四羧酸二酯二氯化物在鹼的存在下進行反應，或使四羧酸二酯與二胺在適當之縮合劑、鹼的存在下進行反應而得到。 Further, the polyphthalate is condensed by a known method by reacting a diamine component with a tetracarboxylic acid diester dichloride in the presence of a base or by appropriately condensing a tetracarboxylic acid diester with a diamine. It is obtained by carrying out a reaction in the presence of a solvent and a base.

<聚醯胺酸酯> <Polyurethane>

本發明所使用的可溶性聚醯胺酸酯係具有以下述之式(2)所表示的結構。 The soluble polyphthalate used in the present invention has a structure represented by the following formula (2).

於上述式(2)中，R1為碳數1~5之烷基。 In the above formula (2), R 1 is an alkyl group having 1 to 5 carbon atoms.

聚醯胺酸酯係隨著烷基中之碳數增加，醯亞胺化進行的溫度會跟著提高。因此，就以熱所進行之醯亞胺化的容易度之觀點而言，R1係以碳數1或2之烷基，特別是甲基為佳。 Polyurethane esters increase in temperature as the number of carbon atoms in the alkyl group increases. Therefore, R 1 is preferably an alkyl group having 1 or 2 carbon atoms, particularly a methyl group, from the viewpoint of easiness of the imidization by heat.

於上述式(2)中，X2係與上述式(1)之X1、上述式(2)之Y2係與上述式(1)之Y1分別具有相同的定義。其中，式(2)之X2係具有芳香族結構時，由於所得到的液晶配向膜具有高的電壓保持率特性，故為佳。具有芳香族結構之較佳的X2係可列舉上述之X-26~X-45，特別是以X-26為佳。 In (2) In the above formula, X 2 and X Department of the formula (1) of 1, Y in the formula (2) with the line Y 2 in the formula (1) of 1 have the same definitions. When the X 2 type of the formula (2) has an aromatic structure, the obtained liquid crystal alignment film preferably has high voltage holding ratio characteristics. Preferred X 2 systems having an aromatic structure include the above X-26 to X-45, and particularly preferably X-26.

於上述式(2)中，A1及A2係各自獨立為氫原子、或可具有取代基之碳數1~10之烷基、烯基或炔基。 In the above formula (2), A 1 and A 2 each independently represent a hydrogen atom or an alkyl group, an alkenyl group or an alkynyl group having 1 to 10 carbon atoms which may have a substituent.

可具有取代基之碳數1~10之烷基的具體例係可列舉：甲基、乙基、丙基、丁基、t-丁基、己基、辛基、癸基、環戊基、環己基、雙環己基等。 Specific examples of the alkyl group having 1 to 10 carbon atoms which may have a substituent include methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group, decyl group, cyclopentyl group and ring. Hexyl, bicyclohexyl and the like.

可具有取代基之碳數1~10之烯基係可列舉將存在於上述烷基的1個以上之CH2-CH2結構取代成CH-CH結構者，更具體而言係可列舉：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 having 1 to 10 carbon atoms which may have a substituent may be a structure in which one or more CH 2 -CH 2 structures present in the above alkyl group are substituted with a CH-CH structure, and more specifically, ethylene may be mentioned. Base, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclopropenyl, cyclopentenyl , cyclohexenyl and the like.

可具有取代基之碳數1~10之炔基係可列舉將存在於前述烷基的1個以上之CH2-CH2結構取代成C≡C結構者，更具體而言係可列舉：乙炔基、1-丙炔基、2-丙炔基等。 The alkynyl group having 1 to 10 carbon atoms which may have a substituent may be a structure in which one or more CH 2 -CH 2 structures present in the alkyl group are substituted with a C≡C structure, and more specifically, acetylene may be mentioned. Base, 1-propynyl, 2-propynyl and the like.

A1及A2係以各自獨立為氫原子、甲基、乙基、乙稀基、烯丙基為佳，以氫原子、甲基為更佳。 A 1 and A 2 are each independently a hydrogen atom, a methyl group, an ethyl group, an ethyl group or an allyl group, and more preferably a hydrogen atom or a methyl group.

上述之烷基、烯基、炔基係只要全體碳數為1~10則可具有取代基，亦可進一步藉由取代基而形成環結構。另外，藉由取代基而形成環結構係意味著取代基彼此或取代基與母骨架的一部分鍵結而成為環結構。 The above-mentioned alkyl group, alkenyl group or alkynyl group may have a substituent as long as the total number of carbon atoms is from 1 to 10, and a ring structure may be further formed by a substituent. Further, the formation of a ring structure by a substituent means that the substituents or the substituents are bonded to a part of the parent skeleton to form a ring structure.

以上述式(2)所表示的聚醯胺酸酯係可藉由以下述式(6)~(8)所表示的四羧酸衍生物中任一者與以式(9)所表示的二胺化合物產生反應而得到。 The polyphthalate ester represented by the above formula (2) can be any one of the tetracarboxylic acid derivatives represented by the following formulas (6) to (8) and the two represented by the formula (9). The amine compound is obtained by a reaction.

(上述式中，X2、Y2、R1、A1及A2係各自如同上述所定義)。 (In the above formula, X 2 , Y 2 , R 1 , A 1 and A 2 are each as defined above).

以上述式(2)所表示的聚醯胺酸酯係可以記 載於下的(A)~(C)中任一種方法來進行合成。 The polyamidomate represented by the above formula (2) can be recorded The synthesis is carried out by any of the methods (A) to (C) below.

(A)由聚醯胺酸進行合成的情況 (A) Synthesis by polyproline

聚醯胺酸酯，係可藉由將由四羧酸二酐與二胺所得到的聚醯胺酸予以酯化而加以合成。 The polyglycolate can be synthesized by esterifying a polyamic acid obtained from a tetracarboxylic dianhydride and a diamine.

具體而言，可藉由使聚醯胺酸與酯化劑在有機溶劑的存在下，於-20~150℃，較佳為0~50℃中，反應30分鐘~24小時，較佳為1~4小時而加以合成。 Specifically, the reaction can be carried out for 30 minutes to 24 hours, preferably 1 by using polylysine and an esterifying agent in the presence of an organic solvent at -20 to 150 ° C, preferably 0 to 50 ° C. ~4 hours to synthesize.

酯化劑係以藉由純化而可容易地去除者為佳，可列舉：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-1,3,5-三嗪-2-基)-4-甲基嗎啉氯化物等。其中，以N,N-二甲基甲醯胺二甲基縮醛為佳。 The esterifying agent is preferably one which can be easily removed by purification, and examples thereof include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide diethyl condensate. Aldehyde, 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-triazin-2-yl)-4-methylmorpholine chloride or the like. Among them, N,N-dimethylformamide dimethyl acetal is preferred.

相對於聚醯胺酸之重複單元1莫耳，酯化劑之添加量係以2~6莫耳當量為佳，以3~4莫耳當量為更佳。 The amount of the esterifying agent to be added is preferably 2 to 6 mol equivalents, more preferably 3 to 4 mol equivalents, based on the repeating unit of the polyamic acid.

上述反應中所使用之有機溶劑，就聚合物之 溶解性的觀點而言，以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、γ-丁內酯為佳，此等亦可1種或將2種以上混合使用。 The organic solvent used in the above reaction, in terms of polymer From the viewpoint of solubility, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and γ-butyrolactone are preferred, and these may be used alone or in combination of two or more. use.

合成時之聚合物的濃度，就不易引起聚合物之析出，且容易得到高分子量體的觀點而言，以1~30質量%為佳，以5~20質量%為更佳。 The concentration of the polymer at the time of synthesis is less likely to cause precipitation of the polymer, and from the viewpoint of easily obtaining a high molecular weight body, it is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass.

(B)藉由四羧酸二酯二氯化物與二胺產生反應而進行合成的情況 (B) Synthesis by reaction of tetracarboxylic acid diester dichloride with diamine

聚醯胺酸酯係可由四羧酸二酯二氯化物與二胺來進行合成。 Polyurethane esters can be synthesized from tetracarboxylic acid diester dichlorides and diamines.

具體而言，可藉由使四羧酸二酯二氯化物與二胺在鹼與有機溶劑的存在下，於-20~150℃，較佳為0~50℃中，反應30分鐘~24小時，較佳為1~4小時而加以合成。 Specifically, the reaction can be carried out for 30 minutes to 24 hours by using a tetracarboxylic acid diester dichloride and a diamine in the presence of a base and an organic solvent at -20 to 150 ° C, preferably 0 to 50 ° C. It is preferably synthesized in 1 to 4 hours.

鹼，雖可使用吡啶、三乙基胺、4-二甲基胺基吡啶等，但為了適度地進行反應，以吡啶為佳。 As the base, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used, but in order to carry out the reaction moderately, pyridine is preferred.

鹼之添加量，就容易去除的量，且容易得到高分子量體的觀點而言，以相對於四羧酸二酯二氯化物為2~4倍莫耳為佳，以2~3倍莫耳為更佳。 The amount of the base to be added is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride, and is 2 to 3 times the molar amount from the viewpoint of easily obtaining a high molecular weight body. For better.

上述反應所使用之有機溶劑，就單體及聚合物之溶解性的觀點而言，以N-甲基-2-吡咯啶酮、γ-丁內酯為佳，此等亦可1種或將2種以上混合使用。 The organic solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the monomer and the polymer, and may be one or the like. Two or more types are used in combination.

合成時之聚合物的濃度，就不易引起聚合物之析出，且容易得到高分子量體的觀點而言，以1~30質量%為佳，以5~20質量%為更佳。 The concentration of the polymer at the time of synthesis is less likely to cause precipitation of the polymer, and from the viewpoint of easily obtaining a high molecular weight body, it is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass.

此外，為了防止四羧酸二酯二氯化物之水解，聚醯胺酸酯之合成所使用的有機溶劑係以儘可能經脫水為佳，且以在氮環境中，防止外氣之混入為佳。 Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the organic solvent used for the synthesis of the polyglycolate is preferably dehydrated as much as possible, and it is preferable to prevent the incorporation of outside air in a nitrogen atmosphere. .

(C)由四羧酸二酯與二胺來合成聚醯胺酸的情況 (C) Synthesis of polylysine from tetracarboxylic acid diester and diamine

聚醯胺酸酯係可藉由將四羧酸二酯與二胺進行聚縮合而加以合成。 Polyammonium esters can be synthesized by polycondensation of a tetracarboxylic acid diester with a diamine.

具體而言，可藉由使四羧酸二酯與二胺在縮合劑、鹼、及有機溶劑的存在下，於0~150℃，較佳為0~100℃中，反應30分鐘~24小時，較佳為3~15小時而加以合成。 Specifically, the reaction can be carried out for 30 minutes to 24 hours by using a tetracarboxylic acid diester and a diamine in the presence of a condensing agent, a base, and an organic solvent at 0 to 150 ° C, preferably 0 to 100 ° C. It is preferably synthesized in 3 to 15 hours.

縮合劑，係可使用三苯基亞磷酸鹽、二環己基碳二醯亞胺、1-乙基-3-(3-二甲基胺基丙基)碳二醯亞胺鹽酸鹽、N,N'-羰基二咪唑、二甲氧基-1,3,5-三基甲基嗎啉、 O-(苯并***-1-基)-N,N,N’,N’-四甲基脲四氟硼酸鹽、O-(苯并***-1-基)-N,N,N’,N’-四甲基脲六氟磷酸鹽、(2,3-二羥基-2-硫基-3-苯并***基)膦酸二苯基等。 As the condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide 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'-tetramethylurea hexafluorophosphate, (2,3-dihydroxy-2-thio-3-benzo Triazolyl) phosphonic acid diphenyl and the like.

相對於四羧酸二酯，縮合劑之添加量係以2~3倍莫耳為佳，以2~2.5倍莫耳為更佳。 The amount of the condensing agent added is preferably 2 to 3 times the molar amount, more preferably 2 to 2.5 times the molar amount, relative to the tetracarboxylic acid diester.

鹼係可使用吡啶、三乙基胺等之3級胺。 As the base, a tertiary amine such as pyridine or triethylamine can be used.

鹼之添加量，就容易去除的量，且容易得到高分子量體的觀點而言，以相對於二胺成分為2~4倍莫耳為佳，以2~3倍莫耳為更佳。 The amount of the base to be added is preferably from 2 to 4 moles per mole of the diamine component, and more preferably from 2 to 3 moles, from the viewpoint of easily obtaining a high molecular weight body.

上述反應所使用之有機溶劑，就單體及聚合物之溶解性的觀點而言，以N-甲基-2-吡咯啶酮、γ-丁內酯為佳，此等亦可1種或將2種以上混合使用。 The organic solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the monomer and the polymer, and may be one or the like. Two or more types are used in combination.

此外，於上述反應中，藉由添加路易士酸作為添加劑而有效率地進行反應。路易士酸係以氯化鋰、溴化鋰等之鹵化鋰為佳。路易士酸之添加量係以相對於二胺成分為0~1.0倍莫耳為佳，以0.2~0.5倍莫耳為更佳。 Further, in the above reaction, the reaction is efficiently carried out by adding Lewis acid as an additive. The Lewis acid is preferably lithium halide such as lithium chloride or lithium bromide. The addition amount of Lewis acid is preferably 0 to 1.0 times the molar amount of the diamine component, and more preferably 0.2 to 0.5 times the molar amount.

上述3個聚醯胺酸酯之合成方法中，由於可得到高分子量之聚醯胺酸酯，因此以上述(A)或上述(B)之合成法特別佳。 In the method for synthesizing the above three polyglycolates, since the high molecular weight polyglycolate can be obtained, the synthesis method of the above (A) or (B) is particularly preferable.

如上述方法所得到的聚醯胺酸酯之溶液，係藉由一邊妥善攪拌一邊注入不良溶劑，而可使聚合物析出。進行數次析出，並以不良溶劑洗淨後，經常溫或進行加熱乾燥，而可得到經純化的聚醯胺酸酯之粉末。 The solution of the polyglycolate obtained by the above method can be precipitated by injecting a poor solvent while stirring well. After several times of precipitation and washing with a poor solvent, the powder of the purified polyphthalate is obtained by heating or drying it frequently.

不良溶劑雖無特別限定，但可列舉：水、甲醇、乙 醇、己烷、丁基賽路蘇、丙酮、甲苯等，以甲醇、乙醇為佳。 The poor solvent is not particularly limited, but examples thereof include water, methanol, and B. Alcohol, hexane, butyl sarbuta, acetone, toluene, etc., preferably methanol or ethanol.

<液晶配向處理劑> <Liquid alignment treatment agent>

本發明之液晶配向處理劑係含有以上述式(1)所表示之可溶性聚醯亞胺與以上述式(2)所表示之聚醯胺酸酯。一般，本發明之液晶配向處理劑係為可溶性聚醯亞胺及聚醯胺酸酯(以下，有時統稱為聚合物)溶解於有機溶劑中的溶液之狀態。只要是具有該溶液之形態，則於例如將聚醯胺酸酯及/或聚醯胺酸在有機溶劑中進行合成時，可為所得到的反應溶液本身者，此外，亦可為將此反應溶液在適合的溶劑中加以稀釋者。此外，將聚醯胺酸酯及/或聚醯胺酸作為粉末而得到時，亦可為使此溶解於有機溶劑中而製成溶液者。 The liquid crystal alignment treatment agent of the present invention contains the soluble polyimine represented by the above formula (1) and the polyphthalate represented by the above formula (2). In general, the liquid crystal alignment treatment agent of the present invention is in a state in which a solution of a soluble polyimine and a polyglycolate (hereinafter, collectively referred to as a polymer) is dissolved in an organic solvent. When the form of the solution is used, for example, when the polyglycolate and/or the polyaminic acid are synthesized in an organic solvent, the reaction solution itself may be obtained, or the reaction may be carried out. The solution is diluted in a suitable solvent. Further, when the polyglycolate and/or polyglycolic acid are obtained as a powder, the solution may be prepared by dissolving the solution in an organic solvent.

可溶性聚醯亞胺，對有機溶劑之溶解性的關係上，其重量平均分子量較佳為5,000~200,000，更佳為10,000~100,000。此外，數量平均分子量較佳為5,000~100,000，更佳為10,000~50,000。 The soluble polyimine, in terms of solubility in an organic solvent, preferably has a weight average molecular weight of 5,000 to 200,000, more preferably 10,000 to 100,000. Further, the number average molecular weight is preferably from 5,000 to 100,000, more preferably from 10,000 to 50,000.

另一方面，聚醯胺酸酯之重量平均分子量，較佳為5,000~200,000，更佳為10,000~100,000。此外，數量平均分子量較佳為5,000~100,000，更佳為10,000~50,000。 On the other hand, the weight average molecular weight of the polyphthalate is preferably 5,000 to 200,000, more preferably 10,000 to 100,000. Further, the number average molecular weight is preferably from 5,000 to 100,000, more preferably from 10,000 to 50,000.

本發明之液晶配向處理劑中，前述聚醯亞胺之含量與前述聚醯胺酸酯之含量，係以聚醯胺酸酯/聚醯 胺酸(質量比率)計為1/9~9/1為佳，較佳為2/8~8/2，特別佳為3/7~7/3。藉由使該比率落入此範圍，而可提供液晶配向性與電特性皆為良好的液晶配向處理劑。 In the liquid crystal alignment treatment agent of the present invention, the content of the polyimine and the content of the polyamidolate are polyglycosate/polyfluorene The amine acid (mass ratio) is preferably from 1/9 to 9/1, preferably from 2/8 to 8/2, particularly preferably from 3/7 to 7/3. By setting the ratio within this range, it is possible to provide a liquid crystal alignment treatment agent which is excellent in liquid crystal alignment and electrical properties.

本發明之液晶配向處理劑中，聚合物之含量(濃度)雖可依據欲形成的液晶配向膜之厚度而適當變更，但就形成均勻且無缺陷的塗膜之觀點而言，相對於有機溶劑100質量%，聚合物成分之含量係以0.5質量%以上為佳，就溶液之保存安定性的觀點而言，係以15質量%以下為佳，較佳為1~10質量%。 In the liquid crystal alignment treatment agent of the present invention, the content (concentration) of the polymer may be appropriately changed depending on the thickness of the liquid crystal alignment film to be formed, but from the viewpoint of forming a uniform and defect-free coating film, relative to the organic solvent The content of the polymer component is preferably 0.5% by mass or more, and is preferably 15% by mass or less, and more preferably 1% to 10% by mass, from the viewpoint of storage stability of the solution.

另外，此時，亦可預先製作聚合物的濃度較濃的溶液，當作為液晶配向處理劑時再將該濃厚的溶液加以稀釋。該聚合物成分之濃厚的溶液之濃度係以10~30質量%為佳，以10~15質量%為更佳。 Further, at this time, a solution having a concentrated polymer concentration may be prepared in advance, and when it is used as a liquid crystal alignment treatment agent, the concentrated solution may be diluted. The concentration of the concentrated solution of the polymer component is preferably 10 to 30% by mass, more preferably 10 to 15% by mass.

此外，亦可在將聚合物成分的粉末溶解於有機溶劑而製作溶液時進行加熱。加熱溫度係以20~150℃為佳，以20~80℃特別佳。 Further, heating may be performed when a powder of a polymer component is dissolved in an organic solvent to prepare a solution. The heating temperature is preferably 20 to 150 ° C, and particularly preferably 20 to 80 ° C.

本發明之液晶配向處理劑所含有的有機溶劑係只要聚合物成分為均勻地溶解者則無特別限定。若列舉其具體例則可列舉：N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-甲基己內醯胺、2-吡咯啶酮、N-乙烯基-2-吡咯啶酮、二甲基亞碸、二甲基碸、γ-丁內酯、1,3-二甲基-咪唑啶酮、3-甲氧基-N,N-二甲基丙醯胺等。其中，就溶解性之觀點而言係以N-甲基-吡咯啶酮、N-乙基-吡咯啶 酮等之極性大者為佳。 The organic solvent contained in the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrole. Pyridone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl azine, dimethylhydrazine , γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, and the like. Among them, from the viewpoint of solubility, N-methyl-pyrrolidone and N-ethyl-pyrrolidine It is preferred that the ketone or the like is more polar.

有機溶劑係可1種或將2種以上混合使用。此外，單獨使用時即使為無法均勻地溶解聚合物成分的有機溶劑，只要在聚合物不析出的範圍內，亦可混合使用。 The organic solvent may be used alone or in combination of two or more. Further, even if it is an organic solvent which cannot uniformly dissolve a polymer component at the time of use alone, it may be used in combination as long as it does not precipitate in the range in which the polymer does not precipitate.

本發明之液晶配向處理劑，除了用以使聚合物成分溶解之有機溶劑以外，亦可含有將液晶配向處理劑塗佈於基板時用以使塗膜均一性提昇的溶劑。該溶劑，一般而言係可使用表面張力較上述有機溶劑更低的溶劑。若列舉其具體例則可列舉：乙基賽路蘇、丁基賽路蘇、丁基賽路蘇乙酸酯、乙基卡必醇、丁基卡必醇、乙基卡必醇乙酸酯、乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲基酯、乳酸乙基酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊基酯等。其中，較佳使用有丁基賽路蘇、乙基卡必醇等。此等之溶劑亦可併用2種以上。 The liquid crystal alignment treatment agent of the present invention may contain, in addition to the organic solvent for dissolving the polymer component, a solvent for improving the uniformity of the coating film when the liquid crystal alignment treatment agent is applied to the substrate. As the solvent, generally, a solvent having a lower surface tension than the above organic solvent can be used. Specific examples thereof include ethyl celecoxib, butyl serosol, butyl succinate acetate, ethyl carbitol, butyl carbitol, and ethyl carbitol acetate. , ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol Monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-B Oxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. Among them, butyl sirolius, ethyl carbitol, and the like are preferably used. These solvents may be used in combination of two or more kinds.

於本發明之液晶配向處理劑中，雖有併用用以溶解聚合物成分的上述有機溶劑、與用以提昇塗膜均一性的溶劑之情況，但有機溶劑與溶劑之使用量係以容積比率計為30/70~90/10，較佳為60/40~80/20。 In the liquid crystal alignment treatment agent of the present invention, the above organic solvent for dissolving the polymer component and the solvent for improving the uniformity of the coating film are used in combination, but the organic solvent and the solvent are used in a volume ratio. It is 30/70 to 90/10, preferably 60/40 to 80/20.

此外，本發明之液晶配向處理劑，亦可含有矽烷偶合劑或交聯劑等之各種添加劑。矽烷偶合劑係在提昇塗佈有液晶配向處理劑之基板與形成於其上之液晶配向 膜的密著性之目的下加以添佳。以下雖可列舉矽烷偶合劑之具體例，但並不限定於此等。 Further, the liquid crystal alignment agent of the present invention may contain various additives such as a decane coupling agent or a crosslinking agent. A decane coupling agent is used for lifting a substrate coated with a liquid crystal alignment agent and a liquid crystal alignment formed thereon The adhesion of the film is optimized for the purpose of adhesion. Although specific examples of the decane coupling agent are exemplified below, the invention is not limited thereto.

3-胺基丙基三乙氧基矽烷、3-(2-胺基乙基)胺基丙基三甲氧基矽烷、3-(2-胺基乙基)胺基丙基甲基二甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-苯基胺基丙基三甲氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、3-胺基丙基二乙氧基甲基矽烷等之胺系矽烷偶合劑；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、乙烯基甲基二甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三異丙氧基矽烷、烯丙基三甲氧基矽烷、p-苯乙烯基三甲氧基矽烷等之乙烯基系矽烷偶合劑；3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等之環氧系矽烷偶合劑；3-甲基丙烯醯氧丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷等之甲基丙烯酸系矽烷偶合劑；3-丙烯醯氧基丙基三甲氧基矽烷等之丙烯酸系矽烷偶合劑；3-脲基丙基三乙氧基矽烷等之脲基系矽烷偶合劑；雙(3-(三乙氧基矽烷基)丙基)二硫化物、雙(3-(三乙氧基矽烷基)丙基)四硫化物等之硫化物系矽烷偶合劑；3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-辛醯基硫-1-丙基三乙氧基矽烷等之 巰基系矽烷偶合劑；3-異氰酸酯丙基三乙氧基矽烷、3-異氰酸酯丙基三甲氧基矽烷等之異氰酸酯系矽烷偶合劑；三乙氧基矽烷基丁基醛等之醛系矽烷偶合劑；三乙氧基矽烷基丙基甲基胺甲酸酯、(3-三乙氧基矽烷基丙基)-t-丁基胺甲酸酯等之胺甲酸酯系矽烷偶合劑。 3-aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-(2-aminoethyl)aminopropylmethyldimethoxy Baseline, 3-aminopropyltrimethoxydecane, 3-phenylaminopropyltrimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl-butylene) An amine decane coupling agent such as propylamine or 3-aminopropyldiethoxymethyl decane; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxy phenyl) Oxy) decane, vinyl methyl dimethoxy decane, vinyl triethoxy decane, vinyl triisopropoxy decane, allyl trimethoxy decane, p-styryl trimethoxy decane Vinyl decane coupling agent; 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldi An epoxy-based decane coupling agent such as ethoxy decane, 3-glycidoxypropylmethyldimethoxy decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane; -Methyl propylene oxiranyl methyl dimethoxy decane, 3-methyl propylene oxime propyl a methacrylic decane coupling agent such as trimethoxy decane, 3-methyl propylene methoxypropyl methyl diethoxy decane, 3-methyl propylene oxypropyl triethoxy decane; 3-propene oxime Acrylic decane coupling agent such as oxypropyltrimethoxydecane; urea-based decane coupling agent such as 3-ureidopropyltriethoxydecane; bis(3-(triethoxydecyl)propyl a sulfide-based decane coupling agent such as disulfide or bis(3-(triethoxydecyl)propyl)tetrasulfide; 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyl Trimethoxy decane, 3-octyl thiol-1-propyltriethoxy decane, etc. Mercapto-based decane coupling agent; isocyanate-based decane coupling agent such as 3-isocyanate propyl triethoxy decane or 3-isocyanate propyl trimethoxy decane; aldehyde decane coupling agent such as triethoxy decyl butyl aldehyde An urethane-based decane coupling agent such as triethoxysulfonylpropylmethylamine formate or (3-triethoxydecylpropyl)-t-butylamine formate.

上述矽烷偶合劑的添加量，若過多則未反應的部分會對液晶配向性造成不良影響，若過少則不會發揮對密著性之效果，因此相對於聚合物之固體成分以0.01~5.0質量%為佳，以0.1~1.0質量%為更佳。 When the amount of the above-mentioned decane coupling agent is too large, the unreacted portion adversely affects the liquid crystal alignment property, and if it is too small, the effect of adhesion is not exhibited, so that the solid content of the polymer is 0.01 to 5.0 mass. % is better, preferably 0.1 to 1.0% by mass.

添加上述矽烷偶合劑時，為了防止聚合物析出，以在添加前述用以提昇塗膜均一性之溶劑之前進行添加為佳。此外，添加矽烷偶合劑時，係可在將聚醯胺酸酯溶液與聚醯胺酸溶液進行混合之前，添加於聚醯胺酸酯溶液、聚醯胺酸溶液、或者聚醯胺酸酯溶液與聚醯胺酸溶液兩者。此外，可添加於聚醯胺酸酯與聚醯胺酸之混合溶液中。 When the above decane coupling agent is added, in order to prevent precipitation of the polymer, it is preferred to add it before adding the solvent for improving the uniformity of the coating film. In addition, when the decane coupling agent is added, it may be added to the polyphthalate solution, the polyaminic acid solution, or the polyamidate solution before mixing the polyphthalate solution with the polyaminic acid solution. Both with polyamic acid solutions. Further, it may be added to a mixed solution of a polyperurethane and a polyamic acid.

矽烷偶合劑係在提昇聚合物與基板之密著性的目的下進行添加，因此矽烷偶合劑之添加方法，係以添加於能夠遍佈存在膜內部及基板界面的聚醯胺酸溶液，使聚合物與矽烷偶合劑充分反應之後，與聚醯胺酸酯溶液進行混合的方法為更佳。 The decane coupling agent is added for the purpose of improving the adhesion between the polymer and the substrate. Therefore, the method of adding the decane coupling agent is added to a polylysine solution which can be distributed throughout the film and at the substrate interface to polymerize the polymer. After sufficiently reacting with the decane coupling agent, a method of mixing with the polyphthalate solution is more preferable.

將本發明之液晶配向處理劑塗佈於基板之後，為了在將塗膜燒成時有效率地進行聚醯胺酸之醯亞胺化，亦可添加醯亞胺化促進劑。 After the liquid crystal alignment treatment agent of the present invention is applied to a substrate, a ruthenium imidization accelerator may be added in order to efficiently carry out the ruthenium imidization of the polyamine acid when the coating film is fired.

以下雖可列舉聚醯胺酸酯之醯亞胺化促進劑的具體 例，但並不限定於此等。 The following may cite specific examples of polyamidomate oxime imidization accelerators. For example, it is not limited to this.

上述式(B-1)~(B-17)中之D，係各自獨立為tert-丁氧基羰基、或9-茀基甲氧基羰基。另外，於(B-14)~(B-17)中，雖一個式中存在複數個D，但此等可彼此相同或相異。 D in the above formulae (B-1) to (B-17) is each independently a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. Further, in (B-14) to (B-17), although a plurality of Ds exist in one formula, these may be the same or different from each other.

雖只要在能得到促進聚醯胺酸酯之熱醯亞胺的效果之範圍內，則醯亞胺化促進劑的含量並不特別限制，但相對於液晶配向處理劑中之聚醯胺酸酯所含有的下述式(12) 之醯胺酸酯部位1莫耳，較佳為0.01莫耳以上，更佳為0.05莫耳以上，再更佳為0.1莫耳以上。此外，就使燒成後之膜中所殘留的醯亞胺化促進劑自體對液晶配向膜之所有特性所造成的不良影響抑制在最小限度之觀點而言，相對於液晶配向處理劑中之聚醯胺酸酯所含有的下述式(12)之醯胺酸酯部位1莫耳，促進劑較佳為2莫耳以下，更佳為1莫耳以下，再更佳為0.5莫耳以下。 The content of the ruthenium iodide promoter is not particularly limited as long as it is within the range in which the effect of the heat oxime imine for promoting the polyphthalate is obtained, but it is relative to the polyphthalate in the liquid crystal alignment treatment agent. Contains the following formula (12) The glutamate moiety is 1 mole, preferably 0.01 mole or more, more preferably 0.05 mole or more, still more preferably 0.1 mole or more. In addition, the effect of suppressing the adverse effects of the ruthenium iodide promoter remaining in the film after firing on all the properties of the liquid crystal alignment film is minimized with respect to the liquid crystal alignment treatment agent. The phthalate moiety of the following formula (12) contained in the polyglycolate is 1 mol, and the accelerator is preferably 2 mol or less, more preferably 1 mol or less, still more preferably 0.5 mol or less. .

添加醯亞胺化促進劑時，由於具有因加熱而進行醯亞胺化的可能性，因此較佳為在利用良溶劑及不良溶劑加以稀釋之後添加。 When the ruthenium iodide promoter is added, since it is likely to be imidized by heating, it is preferably added after being diluted with a good solvent and a poor solvent.

<液晶配向膜> <Liquid alignment film>

本發明之液晶配向膜係將上述液晶配向處理劑塗佈於基板，經乾燥之後，進行燒成所得到的膜。 In the liquid crystal alignment film of the present invention, the liquid crystal alignment treatment agent is applied onto a substrate, dried, and then fired.

作為塗佈本發明之液晶配向處理劑的基板係只要是透明性高的基板則無特別限定，可使用玻璃基板、氮化矽基板、丙烯酸基板或聚碳酸酯基板等之塑膠基板等，就製程之簡單化的觀點而言以使用形成有用來液晶驅動之ITO電 極等的基板為佳。此外，於反射型之液晶顯示元件中，若僅為單側之基板則即便是矽晶圓等不透明者亦可使用，此時之電極亦可使用鋁等讓光反射的材料。 The substrate to which the liquid crystal alignment agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate or a polycarbonate substrate can be used. From the point of view of simplification, the use of ITO electricity for liquid crystal driving is used. A very good substrate is preferred. Further, in the reflective liquid crystal display device, if it is only a single-sided substrate, it can be used even if it is opaque such as a germanium wafer. In this case, a material such as aluminum that reflects light can be used.

本發明之液晶配向處理劑之塗佈方法係可列舉：旋轉塗佈法、印刷法、噴墨法等。塗佈本發明之液晶配向處理劑後的乾燥、燒成步驟係可選擇任意的溫度與時間。一般，為了將所含有的有機溶劑充分去除，在50~120℃下進行1分鐘~10分鐘，較佳為在60~100℃下進行2~5分鐘乾燥，其後在150~300℃下進行5分鐘~120分鐘，較佳為在180~230℃下進行10分鐘~60分鐘燒成。 The coating method of the liquid crystal alignment treatment agent of the present invention may, for example, be a spin coating method, a printing method, an inkjet method or the like. The drying and baking steps after the application of the liquid crystal alignment agent of the present invention can be carried out at any temperature and time. Generally, in order to sufficiently remove the organic solvent contained, it is carried out at 50 to 120 ° C for 1 minute to 10 minutes, preferably at 60 to 100 ° C for 2 to 5 minutes, and then at 150 to 300 ° C. 5 minutes to 120 minutes, preferably at 180 to 230 ° C for 10 minutes to 60 minutes.

燒成後之塗膜的厚度雖無特別限定，但若過薄則會有液晶顯示元件之信賴性降低的情況，故為5~300nm、較佳為10~200nm。 Although the thickness of the coating film after baking is not particularly limited, if the thickness of the liquid crystal display device is too small, the reliability of the liquid crystal display device is lowered, so that it is 5 to 300 nm, preferably 10 to 200 nm.

將所得到的液晶配向膜進行配向處理的方法雖可列舉摩擦法、光配向處理法等，但本發明之液晶配向處理劑係於以摩擦法進行使用的情況中特別有用。 The method of performing the alignment treatment on the obtained liquid crystal alignment film may be, for example, a rubbing method or a photo-alignment treatment method. However, the liquid crystal alignment treatment agent of the present invention is particularly useful in the case of being used by a rubbing method.

[液晶顯示元件] [Liquid Crystal Display Element]

本發明之液晶顯示元件，係為藉由上述之手法而由本發明之液晶配向處理劑得到附液晶配向膜的基板，進行配向處理之後，利用習知的方法來製作液晶胞而製成液晶顯示元件者。 In the liquid crystal display device of the present invention, the liquid crystal alignment element is obtained from the liquid crystal alignment treatment agent of the present invention by the above-described method, and after the alignment treatment, the liquid crystal cell is produced by a known method to form a liquid crystal display element. By.

液晶胞之製造方法雖無特別限定，但一般而言，若列 舉一例，則為將形成有液晶配向膜的1對基板，以液晶配向膜面為內側的方式，挾持較佳為1~30μm，更佳為2~10μm的間隔物加以設置之後，以密封劑將周圍固定，注入液晶予以密封的方法。 The method for producing the liquid crystal cell is not particularly limited, but generally, if For example, a pair of substrates on which a liquid crystal alignment film is formed may be provided with a spacer of preferably 1 to 30 μm, more preferably 2 to 10 μm, so that the liquid crystal alignment film surface is inside. A method of fixing the periphery and injecting a liquid crystal to seal it.

針對液晶封入的方法並無特別限制，可例示在使所製作出的液晶胞內減壓後注入液晶的真空法、在滴下液晶後進行密封的滴下法等。 The method of encapsulating the liquid crystal is not particularly limited, and a vacuum method in which liquid crystals are decompressed in the liquid crystal cell to be produced, a liquid drop method in which liquid crystal is dropped, and a sealing method in which liquid crystal is sealed can be exemplified.

實施例 Example

以下，列舉實施例，進一步具體地說明本發明。但，本發明當然不受此等實施例所限定解釋。 Hereinafter, the present invention will be specifically described by way of examples. However, the invention is of course not to be construed as being limited by the embodiments.

另外，實施例及比較例所使用的略稱、及各特性的測量方法係如下所述。 In addition, the abbreviations used in the examples and comparative examples, and the measurement methods of the respective characteristics are as follows.

(四羧酸二酐) (tetracarboxylic dianhydride)

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

PMDA：2,5-雙(甲氧基羰基)對苯二甲酸 PMDA: 2,5-bis(methoxycarbonyl)terephthalic acid

TDA：3,4-二羧基-1,2,3,4-四氫-1-萘琥珀酸二酐 TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride

(二羧酸二酯) (dicarboxylic acid diester)

CBDE：2,4-雙(甲氧基羰基)環丁烷1,3-二羧酸 CBDE: 2,4-bis(methoxycarbonyl)cyclobutane 1,3-dicarboxylic acid

PMDE：2,5-雙(甲氧基羰基)對苯二甲酸 PMDE: 2,5-bis(methoxycarbonyl)terephthalic acid

(二胺) (diamine)

Me-DADPA：N1-(4-胺基苯基)-N1-甲基苯-1,4-二胺 Me-DADPA: N1-(4-aminophenyl)-N1-methylbenzene-1,4-diamine

DADPA：4,4’-二胺基二苯基胺 DADPA: 4,4'-diaminodiphenylamine

p-PDA：p-伸苯基二胺 p-PDA: p-phenylenediamine

DDM：4,4’-二胺基二苯基甲烷 DDM: 4,4'-diaminodiphenylmethane

B76：2,4-二胺基-N,N-二烯丙基苯胺 B76: 2,4-Diamino-N,N-diallylaniline

3-ABA：3-(胺基甲基)苯胺 3-ABA: 3-(Aminomethyl)aniline

C16DAB：4-十六基氧基-1,3-二胺基苯 C16DAB: 4-hexadecyloxy-1,3-diaminobenzene

C18DAB：4-十八基氧基-1,3-二胺基苯 C18DAB: 4-octadecyloxy-1,3-diaminobenzene

(縮合劑) (condensing agent)

DMT-MM：4-(4,6-二甲氧基-1,3,5-三嗪-2-基)-4-甲基嗎啉-4-鎓 DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholin-4-indole

(有機溶劑) (Organic solvents)

NMP：N-甲基-2-吡咯啶酮 NMP: N-methyl-2-pyrrolidone

BC：丁基賽路蘇 BC: Butyl Cyrus

γ-BL：γ-丁內酯 γ-BL: γ-butyrolactone

(實施例1) (Example 1) CBDA(70)PMDA/B76(30)3ABA(50)APC16 CBDA (70) PMDA/B76 (30) 3ABA (50) APC16

使用作為四羧酸二酐成分之CBDA 13.53g(0.069mol)、PMDA 6.54g(0.030mol)；作為二胺成分之B76 6.10g(0.030mol)、3-ABA 6.11g(0.050mol)、C18DAB 6.96g(0.020mol)，於NMP 222.39g中，在室溫下進行反應24小時而得到聚醯胺酸溶液(PAA-1)。 Using CBDA as a tetracarboxylic dianhydride component, 13.53 g (0.069 mol), PMDA 6.54 g (0.030 mol); as a diamine component, B76 6.10 g (0.030 mol), 3-ABA 6.11 g (0.050 mol), C18DAB 6.96 g (0.020 mol) was reacted at room temperature for 24 hours in NMP 222.39 g to obtain a polyaminic acid solution (PAA-1).

於聚醯胺酸溶液(PAA-1)20.00g中，添加 NMP 30.00g、乙酸酐3.90g、及吡啶1.81g，在室溫下攪拌30分鐘之後，以50℃攪拌3小時使其反應。反應結束後，緩緩注入195g之甲醇中，使聚合物析出之後，進行攪拌30分鐘，藉由過濾而回收固體。以甲醇充分洗淨所得到的個體之後，以100℃使其真空乾操，藉此而得到聚醯亞胺粉末(SPI-1)。此聚醯亞胺之數量平均分子量為13,600，重量平均分子量為33,800，醯亞胺化率為90%。 Add 20.00g of polyaminic acid solution (PAA-1) 30.00 g of NMP, 3.90 g of acetic anhydride, and 1.81 g of pyridine were stirred at room temperature for 30 minutes, and then stirred at 50 ° C for 3 hours to cause a reaction. After completion of the reaction, the mixture was gradually poured into 195 g of methanol to precipitate a polymer, and then stirred for 30 minutes, and the solid was recovered by filtration. The obtained individual was sufficiently washed with methanol, and then vacuum-dried at 100 ° C to obtain a polyimine powder (SPI-1). The polyimine had a number average molecular weight of 13,600, a weight average molecular weight of 33,800, and a ruthenium iodide ratio of 90%.

於聚醯亞胺粉末(SPI-1)6.47g中，添加γ-BL 58.23g，以50℃進行攪拌24小時使其溶解，確認完全溶解。然後，添加γ-BL 15.28g、BC 19.73g，以50℃進行攪拌24小時，以得到聚醯亞胺為6.0質量%、γ-BL為74質量%、BC為20質量%之聚醯亞胺溶液(SPI-1)。所得到的聚醯亞胺溶液係作為液晶配向處理劑(AL-1)。使用此塗佈液進行摩擦耐性、白化、及電壓保持率(VHR)之評估。 58.23 g of γ-BL was added to 6.47 g of polyimine powder (SPI-1), and the mixture was stirred at 50 ° C for 24 hours to be dissolved, and it was confirmed to be completely dissolved. Then, 15.28 g of γ-BL and 19.73 g of BC were added, and the mixture was stirred at 50 ° C for 24 hours to obtain a polybendimimine having a polyamidene content of 6.0% by mass, a γ-BL ratio of 74% by mass, and a BC of 20% by mass. Solution (SPI-1). The obtained polyimine solution was used as a liquid crystal alignment treatment agent (AL-1). The coating liquid was used for evaluation of friction resistance, whitening, and voltage holding ratio (VHR).

使用實施例1之塗佈液所得到的摩擦耐性、白化、及VHR之各評估結果，係彙整為聚合物溶液之組成比而展示於表1。 The evaluation results of the friction resistance, whitening, and VHR obtained by using the coating liquid of Example 1 are shown in Table 1 as a composition ratio of the polymer solution.

(實施例2) (Example 2) TDA/p-PDA(90)APC18 TDA/p-PDA(90)APC18

使用作為四羧酸二酐成分之TDA 7.51g(0.025mol)；作為二胺成分之p-PDA 2.43g(0.023mol)、C18DAB 0.94g(0.0025mol)，於NMP 61.66g中，以 50℃進行反應24小時而得到聚醯胺酸溶液(PAA-2)。 7.51 g (0.025 mol) of TDA as a tetracarboxylic dianhydride component, 2.43 g (0.023 mol) of p-PDA as a diamine component, and 0.94 g (0.0025 mol) of C18DAB, in NMP 61.66 g, The reaction was carried out at 50 ° C for 24 hours to obtain a polyaminic acid solution (PAA-2).

於聚醯胺酸溶液(PAA-2)20.00g中，添加NMP 30.67g、乙酸酐7.18g、吡啶3.33g，在室溫下攪拌30分鐘之後，以40℃攪拌3小時使其反應。反應結束後，緩緩注入214g之甲醇中，使聚合物析出之後，進行攪拌30分鐘，藉由過濾而回收固體。以甲醇充分洗淨所得到的個體之後，以100℃使其真空乾操，藉此而得到聚醯亞胺粉末(SPI-2)。此聚醯亞胺之數量平均分子量為12,400，重量平均分子量為27,400，醯亞胺化率為86%。 To 20.00 g of a polyaminic acid solution (PAA-2), 30.67 g of NMP, 7.18 g of acetic anhydride, and 3.33 g of pyridine were added, and the mixture was stirred at room temperature for 30 minutes, and then stirred at 40 ° C for 3 hours to cause a reaction. After completion of the reaction, 214 g of methanol was gradually injected to precipitate a polymer, and the mixture was stirred for 30 minutes, and a solid was recovered by filtration. The obtained individual was sufficiently washed with methanol, and then vacuum-dried at 100 ° C to obtain a polyimine powder (SPI-2). The polyimine had a number average molecular weight of 12,400, a weight average molecular weight of 27,400, and a ruthenium iodide ratio of 86%.

於聚醯亞胺粉末(SPI-2)2.60g中，添加γ-BL 29.90g，以50℃進行攪拌24小時使其溶解，確認完全溶解。然後，添加γ-BL 2.16g、BC 8.67g，以50℃進行攪拌24小時，以得到聚醯亞胺為6.0質量%、γ-BL為94質量%、BC為20質量%之聚醯亞胺溶液(SPI-2)。所得到的聚醯亞胺溶液係作為液晶配向處理劑(AL-2)。使用此塗佈液進行與實施例1相同之評估。 To 2.60 g of polyimine powder (SPI-2), 29.90 g of γ-BL was added, and the mixture was stirred at 50 ° C for 24 hours to be dissolved, and it was confirmed to be completely dissolved. Then, 2.16 g of γ-BL and 8.67 g of BC were added, and the mixture was stirred at 50 ° C for 24 hours to obtain a polybendimimine having a polyamidene content of 6.0% by mass, a γ-BL of 94% by mass, and a BC of 20% by mass. Solution (SPI-2). The obtained polyimine solution was used as a liquid crystal alignment treatment agent (AL-2). The same evaluation as in Example 1 was carried out using this coating liquid.

(實施例3) (Example 3) CBDE(50)PMDE/DDM CBDE (50) PMDE / DDM

使用作為二羧酸二酯成分之CBDE 11.97g(0.046mol)、PMDE 14.12g(0.050mol)；作為二胺成分之DDM 19.83g(0.10mol)；作為鹼之三乙基胺5.10g(0.050mol)；作為縮合劑之DMT-MM 83.20g(0.30mol)，於NMP 719.18g中，在室溫下進行反應3小時而 得到聚醯胺酸酯溶液(PAE-1)。 Using CBDE as a dicarboxylic acid diester component, 11.97 g (0.046 mol), PMDE 14.12 g (0.050 mol); as a diamine component, DDM 19.83 g (0.10 mol); as a base triethylamine 5.10 g (0.050 mol) ; as a condensing agent, DMT-MM 83.20g (0.30 mol), in NMP 719.18g, the reaction was carried out at room temperature for 3 hours. A polyphthalate solution (PAE-1) was obtained.

將此聚醯胺酸酯溶液投入甲醇4692g中，回收經沉澱的固形物。進而，以甲醇將此固形物進行數次洗淨之後，以100℃予以減壓乾燥，而得到聚醯胺酸酯(PAE-1)之白色粉末。此聚醯胺酸酯之數量平均分子量為12,900，重量平均分子量為28,800。 This polyamine ester solution was poured into 4692 g of methanol, and the precipitated solid matter was recovered. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at 100 ° C to obtain a white powder of poly phthalate (PAE-1). The polyglycolate had a number average molecular weight of 12,900 and a weight average molecular weight of 28,800.

於所得到的聚醯胺酸酯(PAE-1)2.15g中，添加NMP 15.77g，在室溫下進行攪拌4小時。在攪拌結束的時點聚醯胺酸酯係完全溶解。進而，於該溶液中添加NMP 5.47g、及BC 9.20g，在室溫下進行攪拌2小時，而調製出聚醯胺酸酯為6質量%、NMP為74質量%、BC為20質量%之溶液。經調製所得到的聚醯胺酸酯溶液係作為液晶配向處理劑(AL-3)。使用此塗佈液進行與實施例1相同之評估。 To 2.15 g of the obtained polyphthalate (PAE-1), 15.77 g of NMP was added, and the mixture was stirred at room temperature for 4 hours. At the end of the agitation, the polyglycolate was completely dissolved. Further, 5.47 g of NMP and 9.20 g of BC were added to the solution, and the mixture was stirred at room temperature for 2 hours to prepare a polyglycolate of 6 mass%, NMP of 74 mass%, and BC of 20 mass%. Solution. The polyphthalate solution obtained by the preparation was used as a liquid crystal alignment treatment agent (AL-3). The same evaluation as in Example 1 was carried out using this coating liquid.

(實施例4) (Example 4) CBDE/Me-DADPA(50)DADPA(30)DDM CBDE/Me-DADPA(50)DADPA(30)DDM

使用作為二羧酸二酯成分之CBDE 8.57g(0.033mol)；作為二胺成分之Me-DADPA 3.73g(0.018mol)、DADPA 2.10g(0.011mol)、DDM 1.39g(0.0070mol)；作為鹼之三乙基胺1.81g(0.018mol)；作為縮合劑之DMT-MM 25.19g(0.091mol)，於NMP 247.11g中，在室溫下進行反應4小時而得到聚醯胺酸酯溶液(PAE-2)。 8.57 g (0.033 mol) of CBDE as a dicarboxylic acid diester component; 3.73 g (0.018 mol) of Me-DADPA as a diamine component, 2.10 g (0.011 mol) of DADPA, 1.39 g (0.0070 mol) of DDM; 1.81 g (0.018 mol) of triethylamine; 25.19 g (0.091 mol) of DMT-MM as a condensing agent, and reacting at room temperature for 4 hours in NMP 247.11 g to obtain a polyamidate solution (PAE) -2).

將此聚醯胺酸酯溶液投入甲醇1594g中，回 收經沉澱的固形物。進而，以甲醇將此固形物進行數次洗淨之後，以100℃予以減壓乾燥，而得到聚醯胺酸酯(PAE-2)之白色粉末。此聚醯胺酸酯之數量平均分子量為12,300，重量平均分子量為33,500。 The polyphthalate solution was put into 1594 g of methanol, and returned. Recognize the precipitated solids. Further, the solid matter was washed with methanol several times, and then dried under reduced pressure at 100 ° C to obtain a white powder of poly phthalate (PAE-2). The polyglycolate had a number average molecular weight of 12,300 and a weight average molecular weight of 33,500.

於所得到的聚醯胺酸酯(PAE-2)2.18g中，添加NMP 19.62g，在室溫下進行攪拌5小時。在攪拌結束的時點聚醯胺酸酯係完全溶解。進而，於該溶液中添加γ-BL 1.01g、及BC 6.54g，在室溫下進行攪拌1小時，而調製出聚醯胺酸酯為6質量%、γ-BL為57質量%、NMP為17質量%、BC為20質量%之溶液。經調製所得到的聚醯胺酸酯溶液係作為液晶配向處理劑(AL-4)。使用此塗佈液進行與實施例1相同之評估。 To 2.18 g of the obtained polyphthalate (PAE-2), 19.62 g of NMP was added, and the mixture was stirred at room temperature for 5 hours. At the end of the agitation, the polyglycolate was completely dissolved. Further, 1.01 g of γ-BL and 6.54 g of BC were added to the solution, and the mixture was stirred at room temperature for 1 hour to prepare a polyglycolate of 6 mass%, γ-BL of 57 mass%, and NMP. A solution of 17% by mass and BC of 20% by mass. The polyphthalate solution obtained by the preparation was used as a liquid crystal alignment treatment agent (AL-4). The same evaluation as in Example 1 was carried out using this coating liquid.

(實施例5) (Example 5) CBDA(50)PMDA/DDM CBDA (50) PMDA/DDM

使用作為四羧酸二酐成分之CBDA 9.81g(0.050mol)、PMDA 10.25g(0.047mol)；作為二胺成分之DDM 19.83g(0.0060mol)，於γ-BL 113.00g及NMP 113.00g中，在室溫下進行反應3小時而得到聚醯胺酸溶液(PAA-1)。 9.81 g (0.050 mol) of CBDA as a tetracarboxylic dianhydride component, 10.25 g (0.047 mol) of PMDA, 19.83 g (0.0060 mol) of DDM as a diamine component, in γ-BL 113.00 g and NMP 113.00 g, The reaction was carried out at room temperature for 3 hours to obtain a polyaminic acid solution (PAA-1).

使用γ-BL 204.23g、NMP 14.63g、及BC 73.74g來稀釋聚醯胺酸溶液(PAA-1)198.97g，調製出固體成分(聚醯胺酸)為6質量%、γ-BL為59質量%、NMP為20質量%、BC為15質量%之溶液。此聚醯胺酸係數量平 均分子量為20,900，重量平均分子量為57,900。 198.97 g of poly-proline acid solution (PAA-1) was diluted with γ-BL 204.23 g, NMP 14.63 g, and BC 73.74 g to prepare a solid component (polyglycine) of 6 mass% and γ-BL of 59. A solution having a mass %, an NMP of 20% by mass, and a BC of 15% by mass. The polyampinic acid coefficient is flat The average molecular weight was 20,900 and the weight average molecular weight was 57,900.

(實施例6) (Example 6) (實施例1)/(實施例3)=3/7 (Example 1) / (Example 3) = 3/7

以使實施例1所調製出的聚醯亞胺溶液(SPI-1)、與實施例3所調製出的聚醯胺酸酯溶液(PAE-1)之重量比成為30：70的方式進行混合，在室溫下進行攪拌1小時，得到液晶配向處理劑(AL-5)。使用此塗佈液進行與實施例1相同之評估。 The weight ratio of the polyimine solution (SPI-1) prepared in Example 1 to the polyamidomate solution (PAE-1) prepared in Example 3 was 30:70. The mixture was stirred at room temperature for 1 hour to obtain a liquid crystal alignment treatment agent (AL-5). The same evaluation as in Example 1 was carried out using this coating liquid.

(實施例7) (Example 7) (實施例2)/(實施例3)=3/7 (Example 2) / (Example 3) = 3/7

以使實施例1所調製出的聚醯亞胺溶液(SPI-2)、與實施例3所調製出的聚醯胺酸酯溶液(PAE-1)之重量比成為30：70的方式進行混合，在室溫下進行攪拌1小時，得到液晶配向處理劑(AL-6)。使用此塗佈液進行與實施例1相同之評估。 The weight ratio of the polyimine solution (SPI-2) prepared in Example 1 to the polyamidomate solution (PAE-1) prepared in Example 3 was 30:70. The mixture was stirred at room temperature for 1 hour to obtain a liquid crystal alignment agent (AL-6). The same evaluation as in Example 1 was carried out using this coating liquid.

(實施例8) (Example 8) (實施例1)/(實施例4)=3/7 (Example 1) / (Example 4) = 3/7

以使實施例1所調製出的聚醯亞胺溶液(SPI-1)、與實施例4所調製出的聚醯胺酸酯溶液(PAE-2)之重量比成為30：70的方式進行混合，在室溫下進行攪拌1小時，得到液晶配向處理劑(AL-7)。使用此塗佈液進行與 實施例1相同之評估。 The weight ratio of the polyimine solution (SPI-1) prepared in Example 1 to the polyamidomate solution (PAE-2) prepared in Example 4 was 30:70. The mixture was stirred at room temperature for 1 hour to obtain a liquid crystal alignment agent (AL-7). Use this coating solution for The same evaluation as in Example 1.

(實施例9) (Example 9) (實施例2)/(實施例4)=3/7 (Example 2) / (Example 4) = 3/7

以使實施例2所調製出的聚醯亞胺溶液(SPI-2)、與實施例4所調製出的聚醯胺酸酯溶液(PAE-2)之重量比成為30：70的方式進行混合，在室溫下進行攪拌1小時，得到液晶配向處理劑(AL-8)。使用此塗佈液進行與實施例1相同之評估。 The weight ratio of the polyimine solution (SPI-2) prepared in Example 2 to the polyamidomate solution (PAE-2) prepared in Example 4 was 30:70. The mixture was stirred at room temperature for 1 hour to obtain a liquid crystal alignment agent (AL-8). The same evaluation as in Example 1 was carried out using this coating liquid.

(比較例1) (Comparative Example 1) (實施例2)/(實施例5)=3/7 (Example 2) / (Example 5) = 3/7

以使實施例2所調製出的聚醯亞胺溶液(SPI-2)、與實施例5所調製出的聚醯胺酸溶液(PAA-1)之重量比成為30：70的方式進行混合，在室溫下進行攪拌1小時，得到液晶配向處理劑(AL-9)。使用此塗佈液進行與實施例1相同之評估。 The weight ratio of the polyimine solution (SPI-2) prepared in Example 2 to the polyaminic acid solution (PAA-1) prepared in Example 5 was 30:70. Stirring was carried out for 1 hour at room temperature to obtain a liquid crystal alignment treatment agent (AL-9). The same evaluation as in Example 1 was carried out using this coating liquid.

<分子量之測量> <Measurement of molecular weight>

藉由聚合反應所得到的聚醯亞胺之分子量，係藉由GPC(常溫凝膠滲透層析儀)裝置來測量該聚醯亞胺，作為聚乙二醇、及聚乙烯氧化物換算值而計算出數量平均分子量與重量平均分子量。 The molecular weight of the polyimine obtained by the polymerization reaction is measured by a GPC (normal temperature gel permeation chromatography) apparatus as a polyethylene glycol and a polyethylene oxide conversion value. The number average molecular weight and the weight average molecular weight were calculated.

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

管柱：Shodex公司製(KD803與KD805之直列) Pipe column: made by Shodex (inline of KD803 and KD805)

管柱溫度：50℃ Column temperature: 50 ° C

溶析液：N,N-二甲基甲醯胺(作為添加劑，溴化鋰-水合物(LiBr．H2O)為30mmol/L(升)，磷酸/無水結晶(o-磷酸)為30mmol/L，四氫呋喃(THF)為10ml/L) Eluent: N,N-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr.H2O) 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/分鐘 Flow rate: 1.0ml/min

檢量線作成用標準樣品：TOSOH CORPORATION製TSK標準聚乙烯氧化物(分子量約900,000、150,000、100,000、及30,000)，及Polymer Laboratories Ltd製聚乙二醇(分子量約12,000、4,000、及1,000)。 A standard sample for the calibration curve was prepared: TSK standard polyethylene oxide (molecular weights of about 900,000, 150,000, 100,000, and 30,000) manufactured by TOSOH CORPORATION, and polyethylene glycol (molecular weights of about 12,000, 4,000, and 1,000) manufactured by Polymer Laboratories Ltd.

<液晶胞之製作> <Production of liquid crystal cell>

針對實施例1~4及6~10所調製出的液晶配向處理劑，以下述的方式製作出液晶胞。 With respect to the liquid crystal alignment treatment agents prepared in Examples 1 to 4 and 6 to 10, liquid crystal cells were produced in the following manner.

將液晶配向處理劑旋轉塗佈於附透明電極之玻璃基板，在70℃之加熱板上70秒鐘使其乾燥之後，在210℃之加熱板上進行燒成10分鐘，而形成膜厚100nm之塗膜。利用輥徑120mm之摩擦裝置並使用嫘縈布，以輥旋轉數1000rpm、輥進行速度50mm/sec、按壓量0.3mm的條件來摩擦此塗膜面，而得到附液晶配向膜之基板。 The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70 ° C for 70 seconds, and then fired on a hot plate at 210 ° C for 10 minutes to form a film thickness of 100 nm. Coating film. Using a rubbing apparatus having a roll diameter of 120 mm and using a crepe cloth, the coating film surface was rubbed under the conditions of a roller rotation number of 1000 rpm, a roll speed of 50 mm/sec, and a pressing amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film.

接著，準備2片此附液晶定配膜之基板，在其中1片的液晶配向膜面上散佈有6μm之間隔物之後，從其上印刷密封劑，在使另1片基板以朝向液晶配向膜面，且摩擦 方向直行的方式貼合之後，使密封劑硬化而製作出空胞。藉由減壓注入法，將液晶MLC-2003(Merck Japan公司製)注入此空胞中，並將注入口封閉而得到扭轉向列型液晶胞。 Next, two sheets of the liquid crystal alignment film are prepared, and after a spacer of 6 μm is spread on one of the liquid crystal alignment film surfaces, the sealant is printed thereon, and the other substrate is oriented toward the liquid crystal alignment film. Face and friction After bonding in a straight direction, the sealant is hardened to produce a hollow cell. Liquid crystal MLC-2003 (manufactured by Merck Japan Co., Ltd.) was injected into the cells by a pressure reduction injection method, and the injection port was closed to obtain a twisted nematic liquid crystal cell.

以下記述所製作出的各液晶胞之物性的測量、及特性的評估方法。 The measurement of the physical properties of each of the produced liquid crystal cells and the method of evaluating the characteristics will be described below.

另外，針對實施例2~4、實施例6~9、及比較例1中之各液晶配向處理劑的組成、各液晶配向膜之物性的測量及特性的評估等之結果係彙整展示於表1。 In addition, the results of the measurement of the physical properties of the liquid crystal alignment treatment agents, the measurement of the physical properties of each liquid crystal alignment film, and the evaluation of the properties of Examples 2 to 4, Examples 6 to 9, and Comparative Example 1 are shown in Table 1. .

<電壓保持率(VHR)之測量> <Measurement of Voltage Retention Rate (VHR)>

所製作出的扭轉向列型液晶胞之電壓保持率的測量係在90℃之溫度下，60μs間施加4V的電壓，測量166.7ms後之電壓，將電壓能夠保持何種程度作為電壓保持率而計算出。 The voltage holding ratio of the produced twisted nematic liquid crystal cell is measured by applying a voltage of 4 V between 60 μs at a temperature of 90 ° C, measuring the voltage after 166.7 ms, and maintaining the voltage as a voltage holding ratio. Calculate.

另外，於電壓保持率之測量中，係使用有TOYO TECHNICA Corporation製之電壓保持率測量裝置(VHR-1)。 Further, in the measurement of the voltage holding ratio, a voltage holding ratio measuring device (VHR-1) manufactured by TOYO TECHNICA Corporation was used.

<積蓄電荷(RDC)之估算> <Estimation of accumulated charge (RDC)>

對於所製作出的扭轉向列型液晶胞，在23℃的溫度下從0V以0.1V間隔施加直流電壓直至1.0V為止，測量在各電壓之閃爍波幅位準，而製成檢量線。5分鐘接地(ground)之後，施加交流電壓3.0V、及直流電壓 5.0V，測量1小時後之閃爍波幅位準，藉由對照預先製作的檢量線而估算RDC(此RDC之估算方法係稱為閃爍參照法)。 The twisted nematic liquid crystal cell thus produced was subjected to a DC voltage application at a voltage of 0.1 V from 0 V to 1.0 V at a temperature of 23 ° C, and the scintillation amplitude level at each voltage was measured to prepare a calibration curve. After 5 minutes of grounding, apply AC voltage 3.0V, and DC voltage At 5.0V, the flicker amplitude level after 1 hour was measured, and the RDC was estimated by comparing the pre-made calibration curve (this RDC estimation method is called scintillation reference method).

在此，RDC(OFF後)係表示剛施加交流電壓3.0V、及直流電壓5.0V 1小時之後的值，RDC(5分鐘後)係表示剛將交流電壓OFF之後、及OFF後30分鐘之積蓄電荷的值。 Here, RDC (after OFF) indicates the value immediately after the application of the AC voltage of 3.0 V and the DC voltage of 5.0 V for 1 hour, and RDC (after 5 minutes) indicates the accumulation immediately after the AC voltage is turned off and 30 minutes after the OFF. The value of the charge.

產業上之可利用性 Industrial availability

若依據本發明之液晶配向處理劑，則可得到即使可溶性聚醯亞胺的醯亞胺化率高，塗膜形成時也不會引起白化現象而印刷性良好，且塗膜之耐摩擦性良好的液晶配向膜，並且所得到的液晶配向膜所具有之電壓保持率(VHR)及積蓄電荷(RDC)等之電特性亦優異，且具有該液晶配向膜之液晶顯示元件，係廣泛用於TN元件、STN元件、TFT液晶元件，進而垂直配向型之液晶顯示元件等。 According to the liquid crystal alignment treatment agent of the present invention, even if the soluble polyimide pigment has a high sulfhydrylation rate, whitening does not occur when the coating film is formed, the printability is good, and the coating film has good abrasion resistance. The liquid crystal alignment film has excellent electrical properties such as voltage holding ratio (VHR) and accumulated charge (RDC), and the liquid crystal display element having the liquid crystal alignment film is widely used for TN. Element, STN element, TFT liquid crystal element, and further vertical alignment type liquid crystal display element.

另外，將2012年3月30日所申請的日本專利申請案2012-082729號之說明書、申請專利範圍、及摘要的全部內容引用於此，作為本發明之說明書的揭示而採用。 In addition, the entire contents of the specification, the patent application, and the abstract of the Japanese Patent Application No. 2012-082729, filed on March 30, 2012, are hereby incorporated by reference.

Claims (15)

一種液晶配向處理劑，其特徵為含有以下述式(1)所表示的可溶性聚醯亞胺、與以下述式(2)所表示的聚醯胺酸酯， (式(1)中，X1為4價之有機基，Y1為2價之有機基；式(2)中，X2為4價之有機基，Y2為2價之有機基，R1為碳數1~5之烷基；A1及A2係各自獨立為氫原子、或可具有取代基之碳數1~10之烷基、烯基或炔基)。 A liquid crystal alignment treatment agent characterized by containing a soluble polyimine represented by the following formula (1) and a polyphthalate represented by the following formula (2). (In the formula (1), X 1 is a tetravalent organic group, Y 1 is a divalent organic group; in the formula (2), X 2 is a tetravalent organic group, and Y 2 is a divalent organic group, R 1 is an alkyl group having 1 to 5 carbon atoms; and each of A 1 and A 2 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an alkynyl group which may have a substituent. 如申請專利範圍第1項所記載之液晶配向處理劑，其中式(2)中之R1為甲基。 The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein R 1 in the formula (2) is a methyl group. 如申請專利範圍第1項或第2項所記載之液晶配向處理劑，其中於式(1)、式(2)中之X1及X2係各自獨立為由以下述式所表示之結構中所選出的至少一種， The liquid crystal alignment treatment agent according to the first or second aspect of the invention, wherein X 1 and X 2 in the formula (1) and the formula (2) are each independently a structure represented by the following formula: At least one selected, 如申請專利範圍第1項~第3項中任一項所記載之液晶配向處理劑，其中於式(2)中，X2係具有芳香族環之以下的結構， The liquid crystal alignment treatment agent according to any one of the above aspects, wherein in the formula (2), the X 2 system has a structure of an aromatic ring or less. 如申請專利範圍第1項~第3項中任一項所記載之液晶配向處理劑，其中於式(1)中，X1係具有脂肪族結構或脂環式結構。 The liquid crystal alignment treatment agent according to any one of the items 1 to 3, wherein, in the formula (1), the X 1 system has an aliphatic structure or an alicyclic structure. 如申請專利範圍第1項~第5項中任一項所記載之液晶配向處理劑，其中前述聚醯胺酸酯的重量平均分子量為5,000~200,000。 The liquid crystal alignment treatment agent according to any one of claims 1 to 5, wherein the polyglycolate has a weight average molecular weight of 5,000 to 200,000. 如申請專利範圍第1項~第6項中任一項所記載之液晶配向處理劑，其中前述可溶性聚醯亞胺係具有醯亞胺化率50%以上，且重量平均分子量為5,000~200,000。 The liquid crystal alignment treatment agent according to any one of the preceding claims, wherein the soluble polyamidene has a ruthenium iodide ratio of 50% or more and a weight average molecular weight of 5,000 to 200,000. 如申請專利範圍第1項~第7項中任一項所記載之液晶配向處理劑，其中前述可溶性聚醯亞胺的含量與前述聚醯胺酸酯的含量之比(可溶性聚醯亞胺的含量/聚醯胺酸酯的含量)係以質量比率計為1/9~9/1。 The liquid crystal alignment treatment agent according to any one of the preceding claims, wherein the ratio of the content of the soluble polyimine to the content of the polyamidolate (soluble polyimine) The content/content of the polyglycolate is 1/9 to 9/1 in terms of a mass ratio. 如申請專利範圍第1項~第8項中任一項所記載之 液晶配向處理劑，其中含有用以溶解前述可溶性聚醯亞胺與前述聚醯胺酸酯的有機溶劑，且可溶性聚醯亞胺的含量與聚醯胺酸酯之合計量為0.5~15質量%。 As stated in any of the first to eighth items of the patent application scope a liquid crystal alignment treatment agent comprising an organic solvent for dissolving the soluble polyimine and the polyamic acid ester, and the total content of the soluble polyamidene and the polyamidite is 0.5 to 15% by mass. . 如申請專利範圍第9項所記載之液晶配向處理劑，其中前述有機溶劑係含有由N-甲基-吡咯啶酮、N-乙基-吡咯啶酮、及γ-丁內酯所成之群中所選出的至少1種。 The liquid crystal alignment treatment agent according to claim 9, wherein the organic solvent contains a group of N-methyl-pyrrolidone, N-ethyl-pyrrolidone, and γ-butyrolactone. At least one of the selected ones. 如申請專利範圍第1項~第10項中任一項所記載之液晶配向處理劑，其中進一步含有溶劑。 The liquid crystal alignment treatment agent according to any one of the preceding claims, wherein the solvent further contains a solvent. 如申請專利範圍第11項所記載之液晶配向處理劑，其中前述溶劑為丁基賽路蘇。 The liquid crystal alignment treatment agent according to claim 11, wherein the solvent is butyl siroli. 一種液晶配向膜，其係塗佈如申請專利範圍第1項~第12項中任一項所記載之液晶配向處理劑，並加以燒成所得。 A liquid crystal alignment film obtained by baking the liquid crystal alignment treatment agent according to any one of the first to twelfth aspects of the invention. 如申請專利範圍第13項所記載之液晶配向膜，其中塗佈前述液晶配向處理劑，並加以燒成所得到的塗膜之厚度為5~300nm。 The liquid crystal alignment film according to claim 13, wherein the coating film obtained by applying the liquid crystal alignment agent and baking is 5 to 300 nm in thickness. 一種液晶顯示元件，其係具備如申請專利範圍第13項或第14項所記載之液晶配向膜。 A liquid crystal display element comprising the liquid crystal alignment film according to Item 13 or Item 14 of the patent application.
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