TW201630978A - 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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TW201630978A
TW201630978A TW104135439A TW104135439A TW201630978A TW 201630978 A TW201630978 A TW 201630978A TW 104135439 A TW104135439 A TW 104135439A TW 104135439 A TW104135439 A TW 104135439A TW 201630978 A TW201630978 A TW 201630978A
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Naho Kunimi
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    • 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

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Abstract

Provided are: a liquid crystal alignment agent for obtaining an alignment film suitable for photo-alignment, whereby good after-image characteristics are obtained and bright spots do not occur even with negative liquid crystals; a liquid crystal alignment film; and a liquid crystal display element. A liquid crystal alignment agent containing a polyimide precursor having structural units represented by formula (1) and structural units represented by formula (2), and at least one type of polymer (A) selected from the group consisting of imidized polymers of the polyimide precursor. (In the formulas, X2, X2: formula (X1-1) or (X1-2); R1, R2, R3, R4, and R6 are each independently a hydrogen atom or a C1-4 alkyl group; R5 is a C1-4 alkyl group; and n is an integer of 1-6).

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

本發明係關於適合於光配向法處理的液晶配向劑、由此液晶配向劑所得的液晶配向膜、及使用此液晶配向膜的液晶顯示元件。 The present invention relates to a liquid crystal alignment agent suitable for photo-alignment treatment, a liquid crystal alignment film obtained by the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film.

被使用於液晶電視、液晶顯示器等的液晶顯示元件，一般係在元件內設置有用來控制液晶的配列狀態的液晶配向膜。作為液晶配向膜，主要係使用將以聚醯胺酸(聚醯胺酸)等的聚醯亞胺前驅物或可溶性聚醯亞胺之溶液為主成分的液晶配向劑塗佈於玻璃基板等並燒成而得的聚醯亞胺系之液晶配向膜。現在，依工業上最為普及的方法，該液晶配向膜係藉由以綿、尼龍、聚酯等的布對形成於電極基板上之聚醯亞胺系液晶配向膜表面進行於一方向摩擦的所謂摩擦處理所製作。 A liquid crystal display element used for a liquid crystal television, a liquid crystal display or the like is generally provided with a liquid crystal alignment film for controlling the arrangement state of liquid crystals in the element. As the liquid crystal alignment film, a liquid crystal alignment agent containing a solution of a polyamidene precursor such as polyglycine (polyglycine) or a solution of soluble polyimine as a main component is applied to a glass substrate or the like. A polyimine-based liquid crystal alignment film obtained by firing. Now, according to the most popular method in the industry, the liquid crystal alignment film is rubbed in one direction by a cloth of cotton, nylon, polyester or the like on the surface of the polyimide film of the polyimide film formed on the electrode substrate. Made by friction treatment.

光配向法係作為非摩擦的配向處理方法，亦於工業上具有用簡便的製造製程即可生產之優點。 As a non-friction alignment treatment method, the optical alignment method has the advantage of being industrially produced by a simple manufacturing process.

於IPS(In Plane Switching)驅動方式或FFS(Fringe Field switching)驅動方式之液晶顯示元件中， 藉由使用以光配向法所得的液晶配向膜，相較於以摩擦處理法所得的液晶配向膜而言，可期待液晶顯示元件之對比或視野角特性之提昇等，由於可使液晶顯示元件的性能提昇，故有希望成為受人注目之液晶配向處理方法。 In an IPS (In Plane Switching) driving method or an FFS (Fringe Field switching) driving method, By using the liquid crystal alignment film obtained by the photo-alignment method, compared with the liquid crystal alignment film obtained by the rubbing treatment method, the contrast of the liquid crystal display element or the improvement of the viewing angle characteristic can be expected, and the liquid crystal display element can be obtained. With improved performance, it is hoped to become an eye-catching liquid crystal alignment method.

但，藉由光配向法所得的液晶配向膜，相較於以摩擦處理所得的液晶配向膜而言，係有所謂高分子膜之對於配向方向的異向性為小之問題。若異向性小時，無法得到充分的液晶配向性，作成為液晶顯示元件時，將產生殘影等問題。作為提高藉由光配向法所得的液晶配向膜之異向性之方法，提案有於光照射後，除去因光照射所造成前述聚醯亞胺的主鏈被切斷而生成的低分子量成分。 However, the liquid crystal alignment film obtained by the photo-alignment method has a problem that the anisotropy of the polymer film in the alignment direction is small compared to the liquid crystal alignment film obtained by the rubbing treatment. When the anisotropy is small, sufficient liquid crystal alignment property cannot be obtained, and when it is used as a liquid crystal display element, problems such as image sticking occur. As a method of improving the anisotropy of the liquid crystal alignment film obtained by the photo-alignment method, it is proposed to remove a low-molecular-weight component which is formed by cutting the main chain of the polyimine by light irradiation after light irradiation.

[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2011-107266號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-107266

[非專利文獻] [Non-patent literature]

[非專利文獻1]「液晶光配向膜」、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", Functional Materials, November 1997, Vol.17, No. 11 13-22

於IPS驅動方式或FFS驅動方式之液晶顯示元件中，以往係使用正型液晶，但藉由使用負型液晶，將可減少於電極上部之透過損失、並可提昇對比。若將以光配向法所得的液晶配向膜用於使用負型液晶材料的IPS驅動方式或FFS驅動方式的液晶顯示元件中時，可期待較以往的液晶顯示元件具有更高的顯示性能。 In the liquid crystal display device of the IPS driving method or the FFS driving method, a positive liquid crystal has been conventionally used. However, by using a negative liquid crystal, the transmission loss at the upper portion of the electrode can be reduced, and the contrast can be improved. When the liquid crystal alignment film obtained by the photo-alignment method is used for a liquid crystal display device using an IPS driving method or an FFS driving method of a negative liquid crystal material, higher display performance than conventional liquid crystal display elements can be expected.

但，本發明人研究的結果可得知，以光配向法所得的液晶配向膜若為使用負型液晶材料的液晶顯示元件時，顯示不良(輝點)的產生率為高、且有引起顯示不良之問題。 However, as a result of the study by the present inventors, when the liquid crystal alignment film obtained by the photo-alignment method is a liquid crystal display element using a negative liquid crystal material, the occurrence rate of display defects (glow points) is high and display is caused. Bad problem.

本發明之課題係提供一種適合於光配向法處理的液晶配向劑，其係用來得到光配向用液晶配向膜，即使是使用負型液晶，亦未產生輝點、並可得到良好的殘影特性，以及提供由該液晶配向劑所得的液晶配向膜、及具備該液晶配向劑的液晶顯示元件。 An object of the present invention is to provide a liquid crystal alignment agent suitable for photo-alignment treatment, which is used for obtaining a liquid crystal alignment film for photoalignment, which does not generate a bright spot even when a negative-type liquid crystal is used, and can obtain a good afterimage. The present invention provides a liquid crystal alignment film obtained from the liquid crystal alignment agent and a liquid crystal display element including the liquid crystal alignment agent.

本發明人經重複深入研究之結果發現，包含具有特定構造之聚醯亞胺系聚合物之液晶配向劑，係對於達成上述目的為有效，進而完成本發明。 As a result of intensive studies, the present inventors have found that a liquid crystal alignment agent containing a polyimine-based polymer having a specific structure is effective for achieving the above object, and the present invention has been completed.

本發明為一種液晶配向劑，其特徵係含有選自由聚醯亞胺前驅物及該聚醯亞胺前驅物之醯亞胺化聚合物所成群之至少1種的聚合物(A)，前述聚醯亞胺前驅物係具有下述式(1)所表示之構造單位、與下述式(2) 所表示之構造單位。 The present invention is a liquid crystal alignment agent characterized by containing at least one polymer (A) selected from the group consisting of a polyimide intermediate and a polyimide intermediate of the polyimide precursor. The polyimine precursor system has a structural unit represented by the following formula (1), and the following formula (2) The structural unit represented.

(式(1)、式(2)中，X1及X2係分別獨立為選自由下述式(X1-1)及(X1-2)所表示之構造所成群之至少1種。R1、R2、R3、R4、及R6係分別獨立為氫原子、或碳數1~4的烷基。R5係碳數1~4的烷基，n係1~6的整數) (In the formula (1) and the formula (2), each of X 1 and X 2 is independently at least one selected from the group consisting of the structures represented by the following formulas (X1-1) and (X1-2). , R, R 3, R 4 , and R 6 are each independently a hydrogen atom-based, or based .R 5 carbon atoms alkyl having 1 to 4 carbon atoms in the alkyl group, n is an integer of 1 to 4 lines 1 to 6 1 2 )

依據本發明可提供適合於光配向法處理的液晶配向劑，其係可得到能抑制以往的光配向處理法中所看到的輝點、且照射感度高、具有良好的殘影特性之液晶配向膜。藉由具備有由上述液晶配向劑所得的液晶配向膜， 可提供無顯示不良、且可靠性為高的液晶顯示元件。 According to the present invention, it is possible to provide a liquid crystal alignment agent which is suitable for the photo-alignment treatment, and which can provide a liquid crystal alignment which can suppress the bright spots observed in the conventional photo-alignment treatment method, has high irradiation sensitivity, and has excellent afterimage characteristics. membrane. By providing a liquid crystal alignment film obtained from the above liquid crystal alignment agent, A liquid crystal display element having no display defect and high reliability can be provided.

[實施發明之最佳形態] [Best Mode for Carrying Out the Invention] <特定聚合物> <specific polymer>

本發明之液晶配向劑，如上述般，係含有選自由聚醯亞胺前驅物及該聚醯亞胺前驅物之醯亞胺化聚合物所成群之至少1種的聚合物(本發明中亦稱為特定聚合物(A))，前述聚醯亞胺前驅物係具有下述式(1)與下述式(2)所表示之構造單位。本發明中，式(1)所表示之構造單位與下述式(2)所表示之構造單位可存在於相同的聚醯亞胺前驅物中，又，式(1)所表示之構造單位與下述式(2)所表示之構造單位亦可存在於各別的聚醯亞胺前驅物中。 The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of a polyimide intermediate and a polyimide intermediate of the polyimine precursor as described above (in the present invention) Also referred to as a specific polymer (A)), the polyimine precursor has a structural unit represented by the following formula (1) and the following formula (2). In the present invention, the structural unit represented by the formula (1) and the structural unit represented by the following formula (2) may be present in the same polyimine precursor, and the structural unit represented by the formula (1) The structural unit represented by the following formula (2) may also be present in each of the polyimine precursors.

於上述式(1)、式(2)中之X1、X2、R1、R2的各定義係如同上述般。其中，X1、X2就高感度化及液晶配向性之點而言，以具有前述式(X1-2)者為較佳。R1、R2就藉由加熱而造成醯亞胺化之容易度之點而言，以氫原子、或甲基、乙基為較佳。R3、R4、R6就液晶配向性之點而言，以氫原子為較佳。R5就液晶配向性之觀點而言，以甲基為較佳。又，n就液晶配向性之點而言，以1~3的整數，特別以2為較佳。 The definitions of X 1 , X 2 , R 1 and R 2 in the above formulas (1) and (2) are as described above. Among them, in the case where X 1 and X 2 have high sensitivity and liquid crystal alignment, it is preferred to have the above formula (X1-2). In the case where R 1 and R 2 are easy to be imidized by heating, a hydrogen atom, a methyl group or an ethyl group is preferable. R 3 , R 4 and R 6 are preferably a hydrogen atom in terms of liquid crystal alignment. From the viewpoint of liquid crystal alignment, R 5 is preferably a methyl group. Further, n is preferably an integer of 1 to 3, particularly preferably 2, in terms of liquid crystal alignment.

<聚醯亞胺前驅物之製造-聚醯胺酸之製造> <Manufacture of Polyimine Precursor - Production of Polyamide Acid>

於本發明中具有式(1)所表示之構造單位與式(2)所表示之構造單位之聚醯亞胺前驅物(即，聚醯胺酸)，係藉由以下方法來製造。尚，本發明中具有式(1)所表示之構造單位之聚醯亞胺前驅物、與具有式(2)所表示之構造單位之聚醯亞胺前驅物，係可分別、各別地製造，並藉由將兩者混合來製造。 In the present invention, a polyimine precursor (i.e., polyglycine) having a structural unit represented by the formula (1) and a structural unit represented by the formula (2) is produced by the following method. Further, in the present invention, the polyimine precursor having the structural unit represented by the formula (1) and the polyimine precursor having the structural unit represented by the formula (2) may be separately and separately produced. And made by mixing the two.

又，作為與四羧酸或其二酐縮聚合的二胺，以使用賦予式(1)所表示之構造單位的二胺、與賦予式(2)所表示之構造單位的二胺分別為1種類以上，來製造具有式(1)所表示之構造單位與式(2)所表示之構造單位之聚醯亞胺前驅物為較佳。 In addition, as the diamine which is polycondensed with the tetracarboxylic acid or the dianhydride thereof, the diamine which is a structural unit represented by the formula (1) and the diamine which is a structural unit represented by the formula (2) are each 1 It is preferred to produce a polyimine precursor having a structural unit represented by the formula (1) and a structural unit represented by the formula (2).

此時，使賦予上述式(1)中之X1的四羧酸或其二酐、及賦予上述式(2)中之X2的四羧酸或其二酐、與賦予Y1的二胺及賦予Y2的二胺，在溶劑的存在 下，以-20~150℃、較佳為0~50℃下，以30分鐘~24小時、較佳為1~12小時使其進行縮聚合反應來製造。 In this case, a tetracarboxylic acid or a dianhydride thereof to which X 1 in the above formula (1) or a tetracarboxylic acid or a dianhydride thereof to which X 2 in the above formula (2) is imparted, and a diamine to which Y 1 is imparted are provided. And the diamine to which Y 2 is added is subjected to polycondensation 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 12 hours. To manufacture.

二胺與四羧酸之反應一般係在溶劑中來進行。作為此時所使用的溶劑，只要是可溶解所生成的聚醯亞胺前驅物者即可並無特別限定。下述係舉例使用於反應之溶劑之具體例，但並非被限定於此等的例子中。 The reaction of the diamine with the tetracarboxylic acid is generally 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 exemplified by specific examples of the solvent used in the reaction, but are not limited to the examples.

可舉例如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-咪唑啉酮。又，聚醯亞胺前驅物之溶劑溶解性高時，可使用甲基乙基酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮或下述式[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-dimethyl B Guanidine, dimethyl hydrazine or 1,3-dimethyl-imidazolidinone. Further, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D] can be used. -1]~ The solvent represented by the formula [D-3].

(式[D-1]中D1係表示碳數1~3的烷基，式[D-2]中D2係表示碳數1~3的烷基，式[D-3]中D3係表示碳數1~4的烷基)。 (Formula [D-1] in lines D 1 represents an alkyl group having 1 to 3 carbon atoms of the formula [D-2] based in D 2 represents alkyl having 1 to 3 alkyl group, the formula [D-3] 3 in D It is an alkyl group having a carbon number of 1 to 4).

此等溶劑係可單獨、亦可混合後來使用。進而，即使是無法溶解聚醯亞胺前驅物的溶劑，在不析出所生成的聚醯亞胺前驅物之範圍內，亦可混合於前述溶劑來使用。又，因溶劑中的水分會阻礙聚合反應，且進而造成使所生 成的聚醯亞胺前驅物水解之原因，故溶劑以使用脫水乾燥者為較佳。 These solvents may be used singly or in combination. Further, even a solvent which cannot dissolve the polyimide precursor can be used by mixing the solvent in the range in which the produced polyimide precursor is not precipitated. Moreover, since the water in the solvent hinders the polymerization reaction, and further causes the production The resulting polyimine precursor is hydrolyzed, so that the solvent is preferably dried using dehydration.

又，為了得到聚醯胺酸烷基酯係可使用如下方法：使對羧酸基進行二烷基酯化的四羧酸與1級或2級的二胺化合物進行縮聚合之方法，使對羧酸基進行二烷基酯化的四羧酸二鹵化物與1級或2級的二胺化合物進行縮聚合之方法，或將聚醯胺酸的羧基變換成酯之方法。 Further, in order to obtain a polyalkyl phthalate type, a method of polycondensation of a tetracarboxylic acid which dialkylates a carboxylic acid group with a diamine compound of a 1st or 2nd stage may be used. A method in which a dicarboxylic acid group is subjected to polycondensation of a dialkyl esterified tetracarboxylic acid dihalide and a 1 or 2 grade diamine compound, or a method in which a carboxyl group of a polyproline is converted into an ester.

使二胺成分與四羧酸成分在溶劑中反應時，可舉例如下述方法：攪拌使二胺成分分散或溶解於溶劑中而成的溶液，並直接將四羧酸成分、或使其分散或溶解於溶劑中來作添加之方法，相反地使四羧酸成分分散於溶劑中、或於溶解的溶液中添加二胺成分之方法，交替地添加二胺成分與四羧酸成分之方法等，亦可使用此等中任一方法。又，二胺成分或四羧酸成分分別使用多種並使其反應時，可在預先混合的狀態下產生反應、或可分別地依序反應，進而，使分別地反應的低分子量體產生混合反應而製成聚合物。 When the diamine component and the tetracarboxylic acid component are reacted in a solvent, for example, a method in which a diamine component is dispersed or dissolved in a solvent is stirred, and the tetracarboxylic acid component is directly dispersed or dispersed. A method of adding a dicarboxylic acid component to a solvent or a method of adding a diamine component to a dissolved solution, and a method of alternately adding a diamine component and a tetracarboxylic acid component, etc. You can also use any of these methods. Further, when a plurality of diamine components or tetracarboxylic acid components are used and reacted, they may be reacted in a state of being mixed in advance, or may be sequentially reacted separately, and further, a mixed reaction of the low molecular weight bodies respectively reacted may be produced. And made into a polymer.

此時之聚合溫度係可選擇-20~150℃的任意的溫度，但較佳為-5~100℃的範圍內。又，反應係可以任意的濃度來進行，但若濃度過低時，將變得難以得到高分子量的聚合物，若濃度過高時，因反應液的黏性變得過於高而使均勻的攪拌變為困難。因此，較佳為1~50質量%，又更佳為5~30質量%。反應初期係以高濃度來進行，之後可追加溶劑。 The polymerization temperature at this time may be any temperature of -20 to 150 ° C, but preferably in the range of -5 to 100 ° C. Further, the reaction system can be carried out at any concentration. However, when the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction liquid becomes too high and uniform stirring is caused. It becomes difficult. Therefore, it is preferably from 1 to 50% by mass, and more preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then a solvent can be added.

於聚醯亞胺前驅物之聚合反應中，二胺成分之合計莫耳數與四羧酸成分之合計莫耳數的比係以0.8~1.2為較佳，0.9~1.0為特佳。與一般的縮聚合反應相同地，該莫耳比越接近1.0則所生成的聚醯亞胺前驅物之分子量變得越大。 In the polymerization reaction 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, and particularly preferably 0.9 to 1.0. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyimide intermediate precursor becomes.

於本發明中之聚醯亞胺，係使前述聚醯亞胺前驅物閉環後所得的聚醯亞胺，為了得到該聚醯亞胺，係可使用使前述聚醯胺酸或聚醯胺酸烷基酯閉環從而製成聚醯亞胺之方法。 The polyimine in the present invention is a polyimine obtained by ring-closing the polyimine precursor, and in order to obtain the polyimine, the polylysine or polylysine may be used. A method in which an alkyl ester is ring-closed to form a polyimine.

本發明之聚醯亞胺係醯胺酸基的閉環率(亦稱為醯亞胺化率)並非一定要為100%，可因應用途或目的任意地調整，較佳為50~80%。 The closed-loop ratio (also referred to as the ruthenium imidation ratio) of the polyamidino-proline group of the present invention is not necessarily 100%, and may be arbitrarily adjusted depending on the intended use or purpose, and is preferably 50 to 80%.

作為使聚醯亞胺前驅物醯亞胺化之方法，可舉例將聚醯亞胺前驅物之溶液直接加熱之熱醯亞胺化、或於聚醯亞胺前驅物之溶液中添加觸媒之觸媒醯亞胺化。於溶液中使聚醯亞胺前驅物熱醯亞胺化時之溫度係100~400℃，較佳為120~250℃，以藉由醯亞胺化反應所生成的水除去至體系外，同時來進行者為較佳。反應時間係以30分鐘~4小時為較佳。 As a method for imidating the polyimine precursor ruthenium, a solution in which the solution of the polyimide precursor is directly heated is imidized, or a catalyst is added to the solution of the polyimide precursor. The catalyst is imidized. The temperature at which the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C, preferably 120 to 250 ° C, and the water formed by the hydrazine imidization reaction is removed to the outside of the system. It is better to carry it out. The reaction time is preferably from 30 minutes to 4 hours.

聚醯亞胺前驅物之觸媒醯亞胺化係可於聚醯亞胺前驅物之溶液中，添加鹼性觸媒與酸酐，藉由以-20~250℃、較佳為0~180℃攪拌來進行。反應時間係以30分鐘~4小時為較佳。 The catalyst oxime imidization of the polyimide precursor may be added to the solution of the polyimide precursor with a basic catalyst and an acid anhydride at -20 to 250 ° C, preferably 0 to 180 ° C. Stir it. The reaction time is preferably from 30 minutes to 4 hours.

鹼性觸媒的量係醯胺酸基的0.5~30莫耳倍，較佳為 2~20莫耳倍，酸酐的量係醯胺酸基的1~50莫耳倍。較佳為3~30莫耳倍。作為鹼性觸媒可舉例吡啶、三乙基胺、三甲基胺、三丁基胺或三辛基胺。其中，以吡啶係於進行反應時具有適度的鹼性而為較佳。 The amount of the basic catalyst is 0.5 to 30 moles of the prolyl group, preferably 2 to 20 moles, the amount of anhydride is 1 to 50 moles of prolyl group. It is preferably 3 to 30 moles. As the basic catalyst, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine can be exemplified. Among them, pyridine is preferred because it has a moderate basicity when the reaction is carried out.

作為酸酐可舉例乙酸酐、偏苯三酸酐或苯均四酸酐。其中以使用乙酸酐時於反應結束後易於精製而為較佳。以觸媒醯亞胺化之醯亞胺化率，係可藉由調節觸媒量與反應溫度、反應時間來控制。 As the acid anhydride, acetic anhydride, trimellitic anhydride or pyromellitic anhydride can be exemplified. Among them, in the case of using acetic anhydride, it is preferred to be easily purified after completion of the reaction. The imidization ratio of the imidization of the catalyst oxime 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，回收所生成的聚醯亞胺前驅物或聚醯亞胺時，將反應溶液投入溶劑中使其沉澱即可。作為使用於沉澱之溶劑可舉例甲醇、乙醇、異丙醇、丙酮、己烷、丁基賽璐蘇、庚烷、甲基乙基酮、甲基異丁酮、甲苯、苯、水等。投入溶劑中並使其沉澱的聚合物在過濾回收後，可以在常壓或減壓下常溫乾燥或進行加熱來乾燥。 When 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. The solvent used for the precipitation may, for example, be methanol, ethanol, isopropanol, acetone, hexane, butyl cyanidin, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water or the like. The polymer which has been introduced into the solvent and precipitated is filtered and recovered, and dried at room temperature under normal pressure or reduced pressure or heated to dry.

又，將沉澱回收的聚合物再溶解於溶劑中，若重覆2~10次再沉澱回收之操作，可減少聚合物中之雜質。作為此時之溶劑可舉例如醇類、酮類、烴等，若使用選自由此等的中之3種類以上的溶劑時，因可更進一步提高精製之效率而為較佳。 Further, the precipitate-recovered polymer is redissolved in a solvent, and if it is repeated for 2 to 10 times to reprecipitate and recover, impurities in the polymer can be reduced. The solvent in this case may, for example, be an alcohol, a ketone or a hydrocarbon. When a solvent selected from three or more types selected from the above is used, the efficiency of the purification can be further improved.

對於本發明之特定聚合物(A)，係以使用聚醯胺酸烷基酯為較佳。將製造聚醯胺酸烷基酯之較佳具體的方法表示於下述(1)~(3)中。 For the specific polymer (A) of the present invention, it is preferred to use a polyalkyl phthalate. A preferred specific method for producing a polyalkyl amide is shown in the following (1) to (3).

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

由二胺成分與四羧酸成分來製造聚醯胺酸，且對該羧基(COOH基)作化學反應，即進行酯化反應來製造聚醯胺酸烷基酯之方法。 A method in which a polyaminic acid is produced from a diamine component and a tetracarboxylic acid component, and the carboxyl group (COOH group) is chemically reacted, that is, an esterification reaction is carried out to produce a polyalkyleniminoate.

酯化反應係具體而言為在溶劑的存在下，較佳為-20~150℃，又較佳為0~50℃下，使聚醯胺酸與酯化劑反應較佳為30分鐘~24小時，又較佳為1~4小時。 The esterification reaction is specifically carried out in the presence of a solvent, preferably -20 to 150 ° C, and preferably 0 to 50 ° C, and the reaction of the polyaminic acid with the esterifying agent is preferably 30 minutes to 24 hours. In hours, it is preferably 1 to 4 hours.

作為前述酯化劑係以於酯化反應後可易於除去者為較佳，可舉例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-甲基嗎啉鎓氯化物等。酯化劑之使用量相對於聚醯胺酸之重覆單位1莫耳，以2~6莫耳當量為較佳。其中，以2~4莫耳當量為較佳。 The esterification agent is preferably one which can be easily removed after the esterification reaction, and examples thereof include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide II. Acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dinepentyl butyl acetal, N,N-dimethylformamide -t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyl III Nitroene, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, and the like. The amount of the esterifying agent to be used is preferably 1 to 6 moles per unit of the repeating unit of polyamic acid, and preferably 2 to 6 moles. Among them, 2 to 4 molar equivalents are preferred.

作為使用於前述酯化反應中之溶劑，就聚醯胺酸之對於溶劑之溶解性之點而言，可舉例使用於前述二胺成分與四羧酸成分之反應中之溶劑。其中，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-丁內酯為較佳。溶劑係可以1種或混合2種以上來使用。 The solvent used in the esterification reaction may be, for example, a solvent used in the reaction of the diamine component and the tetracarboxylic acid component in terms of the solubility of the polyamic acid to the solvent. Among them, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferred. The solvent may be used alone or in combination of two or more.

於前述酯化反應之溶劑中的聚醯胺酸之濃度，就不易引起聚醯胺酸之析出之點而言，以1~30質量%為較佳。 其中，以5~20質量%為較佳。 The concentration of the polyaminic acid in the solvent of the esterification reaction is preferably from 1 to 30% by mass in terms of the point at which precipitation of the polyaminic acid is less likely to occur. Among them, 5 to 20% by mass is preferred.

(2)藉由二胺成分與四羧酸二酯二氯化物之反應來製造之方法 (2) A method of producing a reaction of a diamine component and a tetracarboxylic acid diester dichloride

二胺成分與四羧酸二酯二氯化物之反應，具體而言為在鹼與溶劑之存在下，以較佳為-20~150℃，又較佳為0~50℃下，使二胺成分與四羧酸二酯二氯化物反應為較佳30分鐘~24小時，又較佳為1~4小時之方法。 The reaction of the diamine component with the tetracarboxylic acid diester dichloride, specifically, the diamine in the presence of a base and a solvent, preferably -20 to 150 ° C, and preferably 0 to 50 ° C The reaction of the component with the tetracarboxylic acid diester dichloride is preferably carried out for 30 minutes to 24 hours, preferably for 1 to 4 hours.

前述鹼可使用吡啶、三乙基胺、4-二甲基胺基吡啶等。其中，為了穏定地進行反應以吡啶為較佳。鹼之使用量係於前述反應後可容易地除去的量為較佳，相對於四羧酸二酯二氯化物，以2~4倍莫耳為較佳。其中，以2~3倍莫耳為又較佳。 As the base, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used. Among them, pyridine is preferred in order to carry out the reaction in a definite manner. The amount of the base to be used is preferably an amount which can be easily removed after the above reaction, and is preferably 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride. Among them, 2 to 3 times Mo is better.

使用於前述反應之溶劑，就所得的聚合物(即，聚醯胺酸烷基酯)之對於溶劑之溶解性之點而言，可舉例使用於前述二胺成分與四羧酸成分之反應之溶劑。其中，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-丁內酯為較佳。此等溶劑係可以1種或混合2種以上來使用。 The solvent used in the above reaction can be exemplified by the reaction of the above-mentioned diamine component and the tetracarboxylic acid component with respect to the solubility of the obtained polymer (i.e., polyalkyl amide) for the solvent. 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.

於前述反應之溶劑中的聚醯胺酸烷基酯之濃度，就不易引起聚醯胺酸烷基酯之析出之點而言，以1~30質量%為較佳。其中，以5~20質量%為較佳。又，為了防止四羧酸二酯二氯化物的水解，故使用於聚醯胺酸烷基酯之製作之溶劑以盡可能脫水為較佳。進而，前述反 應係於氮環境中進行，以防止外氣的混入為較佳。 The concentration of the polyalkyl amide in the solvent of the above reaction is preferably from 1 to 30% by mass in terms of the point at which precipitation of the polyalkyl amide is less likely to occur. 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 for the production of the polyalkyl phthalate to dehydrate as much as possible. Further, the aforementioned counter It should be carried out in a nitrogen atmosphere to prevent the incorporation of outside air.

(3)藉由二胺成分與四羧酸二酯之反應來製造之方法 (3) A method for producing by reacting a diamine component with a tetracarboxylic acid diester

藉由二胺成分與四羧酸二酯之縮聚合反應來製造之方法，具體而言為在縮合劑、鹼及溶劑之存在下，以0~150℃，又較佳為0~100℃，使二胺成分與四羧酸二酯反應較佳為30分鐘~24小時，又較佳為3~15小時之方法。 a method for producing a polycondensation reaction of a diamine component and a tetracarboxylic acid diester, specifically, in the presence of a condensing agent, a base and a solvent, in the range of 0 to 150 ° C, preferably 0 to 100 ° C, The reaction of the diamine component with the tetracarboxylic acid diester is preferably carried out for 30 minutes to 24 hours, preferably for 3 to 15 hours.

前述縮合劑可使用三苯基亞磷酸酯、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-1,3,5-三嗪基甲基嗎啉鎓、O-(苯并***-1-基)-N,N,N’,N’-四甲基脲四氟硼酸鹽、O-(苯并***-1-基)-N,N,N’,N’-四甲基脲六氟磷酸鹽、(2,3-二氫-2-硫酮基-3-苯并噁唑基)膦酸二苯酯等。縮合劑之使用量相對於四羧酸二酯以2~3倍莫耳為較佳，特別是以2~2.5倍莫耳為較佳。 As the condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'- Tetramethylurea tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2 -Diphenyl ester of thioketo-3-benzoxazolyl)phosphonate. The amount of the condensing agent used is preferably 2 to 3 moles per mole of the tetracarboxylic acid diester, and particularly preferably 2 to 2.5 moles.

前述鹼可使用吡啶、三乙基胺等的3級胺。鹼之使用量以於前述縮聚合反應後可容易地除去的量為較佳，相對於二胺成分以2~4倍莫耳為較佳，特別是以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 an amount which can be easily removed after the polycondensation reaction, and is preferably 2 to 4 moles per mole of the diamine component, particularly preferably 2 to 3 moles.

使用於縮聚合反應之溶劑，就所得的聚合物的聚醯胺酸烷基酯之對於溶劑之溶解性之點而言，可舉例使用於前述二胺成分與四羧酸成分之反應之溶劑。特別是以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-丁內酯為較佳。溶劑係可混合2種以上來使用。 The solvent used in the polycondensation reaction can be exemplified as a solvent for reacting the above diamine component and the tetracarboxylic acid component with respect to the solvent solubility of the obtained polymer polyalkyl amide. In particular, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferred. The solvent may be used in combination of two or more kinds.

又，於上述縮聚合反應中藉由加入路易斯酸來作為添加劑，可使反應有效的進行。作為路易斯酸以氯化鋰、溴化鋰等的鹵化鋰為較佳。路易斯酸之使用量相對於二胺成分，以0.1~10倍莫耳為較佳，特別是以2.0~3.0倍莫耳為又較佳。 Further, by adding a Lewis acid as an additive in the above polycondensation reaction, the reaction can be efficiently carried out. As the Lewis acid, lithium halide such as lithium chloride or lithium bromide is preferred. The Lewis acid is preferably used in an amount of 0.1 to 10 moles per mole of the diamine component, particularly preferably 2.0 to 3.0 moles.

若由上述(1)~(3)之方法所得的聚醯胺酸烷基酯的溶液中來回收聚醯胺酸烷基酯時，將反應溶液投入於溶劑中使其沉澱即可。作為使用於沉澱中之溶劑，可舉例水、甲醇、乙醇、2-丙醇、己烷、丁基賽璐蘇、丙酮、甲苯等。投入於溶劑中並使其沉澱之聚合物，為達除去於前述所使用的添加劑‧觸媒類之目的，用上述溶劑來進行多次洗淨操作為較佳。過濾並回收後，可以在常壓或減壓下常溫乾燥或進行加熱來乾燥。又，若將沉澱回收的聚合物使其再溶解於溶劑中，重覆2~10次的再沉澱回收之操作時，可減少聚合物中之雜質。作為此時之溶劑可舉例如能溶解聚合物之溶劑。 When the polyalkyl phthalate is recovered from the solution of the polyalkyl phthalate obtained by the above methods (1) to (3), the reaction solution may be placed in a solvent to precipitate. As the solvent used in the precipitation, water, methanol, ethanol, 2-propanol, hexane, butyl cyanidin, acetone, toluene, or the like can be exemplified. It is preferred to carry out a plurality of washing operations using the above solvent for the purpose of removing the additive and the catalyst used in the above-mentioned solvent for the purpose of removing the polymer which has been introduced into the solvent and precipitated. After filtration and recovery, it can be dried at normal temperature under normal pressure or reduced pressure or heated to dry. Further, when the polymer recovered by precipitation is redissolved in a solvent, and the operation of reprecipitation recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. The solvent at this time may, for example, be a solvent capable of dissolving the polymer.

本發明之聚醯胺酸烷基酯以前述(1)~(3)的方法中，以(1)或(2)的方法為較佳。 In the method of the above (1) to (3), the polyalkyl amide of the present invention is preferably a method of (1) or (2).

<液晶配向劑> <Liquid alignment agent>

液晶配向劑係用來形成液晶配向膜(亦稱為樹脂被膜)之塗佈溶液、且用來形成含有特定聚合物(A)及溶劑之液晶配向膜之塗佈溶液。液晶配向劑中之特定聚合物(A)之含有量，係可依所設定液晶配向劑的塗佈方法或 目的之液晶配向膜的膜厚來適當變更，以2~10質量%為較佳，特別是以3~7質量%為較佳。另一方面，溶劑之含有量以70~99.9質量%為較佳，以90~98質量%為又較佳。 The liquid crystal alignment agent is a coating solution for forming a coating solution of a liquid crystal alignment film (also referred to as a resin film) and for forming a liquid crystal alignment film containing a specific polymer (A) and a solvent. The content of the specific polymer (A) in the liquid crystal alignment agent may be a coating method of the liquid crystal alignment agent or The film thickness of the intended liquid crystal alignment film is appropriately changed, and is preferably 2 to 10% by mass, particularly preferably 3 to 7% by mass. On the other hand, the content of the solvent is preferably from 70 to 99.9% by mass, more preferably from 90 to 98% by mass.

使用於本發明之液晶配向劑之溶劑係使特定聚合物(A)溶解之溶劑(亦稱為良溶劑)，特別是以有機溶劑為較佳。於下述可舉例良溶劑之具體例，但並非被限定於此等的例中。 The solvent used in the liquid crystal alignment agent of the present invention is a solvent (also referred to as a good solvent) for dissolving the specific polymer (A), and particularly an organic solvent is preferred. Specific examples of the good solvent are exemplified below, but are not limited thereto.

可舉例如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-咪唑啉酮、甲基乙基酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮等。其中，以使用N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、或γ-丁內酯為較佳。 For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl Azulene, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone is preferably used.

進而，若對於特定聚合物(A)的溶劑之溶解性為高時，以使用前述式[D-1]~式[D-3]所表示之溶劑為較佳。 Further, when the solubility in the solvent of the specific polymer (A) is high, it is preferred to use the solvent represented by the above formula [D-1] to formula [D-3].

於液晶配向劑中之良溶劑，以溶劑全體的20~99質量%為較佳，以20~90質量%為又較佳，以30~80質量%為特佳。 The good solvent in the liquid crystal alignment agent is preferably 20 to 99% by mass of the entire solvent, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass.

液晶配向劑只要不損及本發明之效果下，可含有塗佈液晶配向劑時使液晶配向膜之塗膜性或表面平滑性提昇之溶劑(亦稱為不良溶劑)。此等不良溶劑以液晶配向劑中所含之溶劑全體的1~80質量%為較佳。其中，以10~80 質量%為較佳。又較佳者為20~70質量%。 The liquid crystal alignment agent may contain a solvent (also referred to as a poor solvent) which improves the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment agent is applied, as long as the effect of the present invention is not impaired. These poor solvents are preferably from 1 to 80% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, 10~80 The mass % is preferred. More preferably, it is 20 to 70% by mass.

於下述可舉例不良溶劑之具體例，但並非被限定於此等的例中。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、新戊基醇、1-己醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己醇、1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、2-甲基-2,4-戊二醇、2-乙基-1,3-己二醇、二丙醚、二丁醚、二己醚、二噁烷、乙二醇二甲醚、乙二醇二***、乙二醇二丁醚、1,2-丁氧基乙烷、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基***、二乙二醇二丁醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、乙酸3-乙氧基丁酯、乙酸1-甲基戊酯、乙酸2-乙基丁酯、乙酸2-乙基己酯、乙二醇單乙酸酯、乙二醇二乙酸酯、碳酸伸丙酯、碳酸伸乙酯、2-(甲氧基甲氧基)乙醇、乙二醇單丁醚、乙二醇單異戊醚、乙二醇單己醚、2-(己氧基)乙醇、糠醇、二乙二醇、丙二醇、丙二醇單丁醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲醚乙酸酯、二丙二醇、二丙二醇單甲醚、二丙二醇單***、二丙二醇二甲醚、三丙二醇單甲醚、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙 二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、乙酸2-(2-乙氧基乙氧基)乙酯、二乙二醇乙酸酯、三乙二醇、三乙二醇單甲醚、三乙二醇單***、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***、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]~式[D-3]所表示之溶劑等。 Specific examples of the poor solvent can be exemplified below, but are not limited thereto. 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-butane Alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-B Base-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 ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexyl Ketone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoethyl Acid ester, ethylene Alcohol diacetate, propyl carbonate, ethyl carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(Hexoxy)ethanol, decyl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol single Methyl 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, B Glycol monoacetate, ethylene glycol diacetate, diethyl Glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethyl 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, Methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3- Propyl methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, the above formula [D-1] ~ Solvent represented by the formula [D-3].

其中，以使用1-己醇、環己醇、1,2-乙二醇、1,2-丙二醇、丙二醇單丁醚、乙二醇單丁醚或二丙二醇二甲醚為較佳。 Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferably used.

於本發明之液晶配向劑中，以導入具有環氧基、異氰酸酯基、氧雜環丁烷基或環狀碳酸酯基之交聯性化合物、具有選自由羥基、羥基烷基及低階烷氧基烷基所成群之至少1種的取代基之交聯性化合物、或具有聚合性不飽和鍵之交聯性化合物為較佳。此等取代基或聚合性不飽和鍵係有必要於交聯性化合物中具有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 oxetane group or a cyclic carbonate group is introduced, and has a hydroxyl group selected from a hydroxyl group, a hydroxyalkyl group and a lower alkoxy group. A crosslinkable compound having at least one substituent grouped in the group of the alkyl group or a crosslinkable compound having a polymerizable unsaturated bond is preferred. These substituents or polymerizable unsaturated bonds are required to have two or more of the crosslinkable compounds.

作為具有環氧基或異氰酸酯基之交聯性化合物，可舉例如雙酚丙酮縮水甘油醚、酚酚醛環氧樹脂、甲酚酚醛環氧樹脂、三縮水甘油基異氰脲酸酯、四縮水甘油基胺基二亞苯(diphenylene)、四縮水甘油基-m-二甲苯二胺、四縮水甘油基-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、雙酚六氟乙醯 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、三縮水甘油基-p-胺酚、四縮水甘油基間二甲苯二胺、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 tetraglycidyl. Diphenylene, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl ether , triphenyl glycidyl ether ethane, bisphenol hexafluoroacetic acid Diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-double (2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl-m-xylenediamine, 2-(4-(2,3-epoxypropoxyl) Phenyl)-2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane, 1,3-bis(4- (1-(4-(2,3-epoxypropoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-yl) Ethyl ethyl) phenyl) ethyl) phenoxy)-2-propanol and the like.

具有氧雜環丁烷基之交聯性化合物係至少具有2個下述式[4A]所表示之氧雜環丁烷基之化合物。 The crosslinkable compound having an oxetane group is a compound having at least two oxetanyl groups represented by the following formula [4A].

具體而言，可舉例國際公開公報WO2011/132751號(2011.10.27公開)的58~59頁所揭示之式[4a]~式[4k]所表示之交聯性化合物。 Specifically, a crosslinkable compound represented by the formula [4a] to the formula [4k] disclosed in pages 58 to 59 of International Publication WO2011/132751 (published 2011.10.27) can be exemplified.

作為具有環狀碳酸酯基之交聯性化合物，係具有至少2個下述式[5A]所表示之環狀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，可舉例國際公開公報WO2012/014898號(2012.2.2公開)的76~82頁所揭示之式[5-1]~式[5-42]所 表示之交聯性化合物。 Specifically, the formula [5-1] to the formula [5-42] disclosed on pages 76 to 82 of International Publication WO2012/014898 (2012.2.2 publication) can be exemplified. Represents a cross-linking compound.

作為具有選自由羥基及烷氧基所成群之至少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，可舉例如三聚氰胺樹脂、尿素樹脂、胍胺樹脂、甘脲-甲醛樹脂、琥珀醯胺-甲醛樹脂、乙烯尿素-甲醛樹脂等。具體而言，可以使用胺基的氫原子被羥甲基或烷氧基甲基或其兩者所取代的三聚氰胺衍生物、苯并胍胺衍生物、或甘脲。該三聚氰胺衍生物或苯并胍胺衍生物係亦可以二聚物或三聚物的形式所存在。此等係以每1個三嗪環具有平均3個以上6個以下的羥甲基或烷氧基甲基為較佳。 The 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, a guanamine resin, Glycoluril-formaldehyde resin, succinimide-formaldehyde resin, ethylene urea-formaldehyde resin, and the like. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group or both can be used. The melamine derivative or the benzoguanamine derivative may also be present in the form of a dimer or a trimer. These are preferably an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups per one triazine ring.

作為上述三聚氰胺衍生物或苯并胍胺衍生物之例子，係可舉例市售品之每1個三嗪環取代有平均3.7個甲氧基甲基的MX-750、每1個三嗪環取代有平均5.8個甲氧基甲基的MW-30(以上為三和Chemical公司製)或CYMEL 300、301、303、350、370、771、325、327、703、712等的甲氧基甲基化三聚氰胺、CYMEL 235、236、238、212、253、254等的甲氧基甲基化丁氧基甲基化三聚氰胺、CYMEL 506、508等的丁氧基甲基化三聚氰胺、如CYMEL 1141之類的含有羧基之甲氧基甲基化異丁氧基甲基化三聚氰胺、如CYMEL 1123之類的甲氧基甲基化乙氧基甲基化苯并胍胺、如CYMEL 1123-10之類的甲氧基甲基化丁氧基甲基化苯并胍胺、如CYMEL 1128之類的丁氧基甲基化苯并胍胺、如CYMEL 1125-80之類的含 有羧基之甲氧基甲基化乙氧基甲基化苯并胍胺(以上為三井Cyanamid公司製)。又，作為甘脲之例子，可舉例如CYMEL 1170之類的丁氧基甲基化甘脲、如CYMEL 1172之類的羥甲基化甘脲、如Powder link 1174之類的甲氧基羥甲基化甘脲等。 As an example of the above melamine derivative or benzoguanamine derivative, MX-750 having an average of 3.7 methoxymethyl groups per one triazine ring substituted by a commercially available product can be exemplified, and each triazine ring is substituted. MW-30 having an average of 5.8 methoxymethyl groups (the above is manufactured by Sanwa Chemical Co., Ltd.) or methoxymethylmethyl of CYMEL 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methoxymethylated butoxymethylated melamine of melamine, CYMEL 235, 236, 238, 212, 253, 254, etc., butoxymethylated melamine of CYMEL 506, 508, etc., such as CYMEL 1141 a methoxymethylated isobutoxymethylated melamine containing a carboxyl group, a methoxymethylated ethoxymethylated benzoguanamine such as CYMEL 1123, such as CYMEL 1123-10 Methoxymethylated butoxymethylated benzoguanamine, butoxymethylated benzoguanamine such as CYMEL 1128, such as CYMEL 1125-80 Methoxymethylated ethoxymethylated benzoguanamine having a carboxyl group (above, Mitsui Cyanamid Co., Ltd.). Further, examples of the glycoluril include butoxymethylated glycoluril such as CYMEL 1170, methylolated glycoluril such as CYMEL 1172, and methoxyhydroxyl group such as Powder link 1174. Glycolized urea and the like.

作為具有羥基或烷氧基之苯或酚性化合物，可舉例如1,3,5-參(甲氧基甲基)苯、1,2,4-參(異丙氧基甲基)苯、1,4-雙(sec-丁氧基甲基)苯或2,6-二羥基甲基-p-tert-丁酚。 Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxy group include 1,3,5-glycol (methoxymethyl)benzene and 1,2,4-para(isopropoxymethyl)benzene. 1,4-Bis(sec-butoxymethyl)benzene or 2,6-dihydroxymethyl-p-tert-butanol.

更具體而言，可舉例國際公開公報WO2011/132751號(2011.10.27公開)的62~66頁所揭示[6-1]~式[6-48]之交聯性化合物。 More specifically, a crosslinkable compound of [6-1] to [6-48] disclosed in pages 62 to 66 of International Publication WO2011/132751 (published 2011.10.27) can be exemplified.

作為具有聚合性不飽和鍵之交聯性化合物，可舉例如三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、三(甲基)丙烯醯氧基乙氧基三羥甲基丙烷、甘油聚縮水甘油醚聚(甲基)丙烯酸酯等在分子內具有3個聚合性不飽和基之交聯性化合物；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、新戊基二醇二(甲基)丙烯酸酯、環氧乙烷雙酚A型二(甲基)丙烯酸酯、環氧丙烷雙酚型二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、甘油二 (甲基)丙烯酸酯、新戊四醇二(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、鄰苯二甲酸二縮水甘油基酯二(甲基)丙烯酸酯、羥基三甲基乙酸新戊基二醇二(甲基)丙烯酸酯等在分子內具有2個聚合性不飽和基之交聯性化合物；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)丙烯醯氧基-2-羥基丙酯、3-氯-2-羥基丙基(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基磷酸酯、N-羥甲基(甲基)丙烯醯胺等在分子內具有1個聚合性不飽和基之交聯性化合物等。 Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta (methyl). Crosslinkability of three polymerizable unsaturated groups in the molecule, such as acrylate, tris(meth) propylene oxyethoxy trimethylolpropane, glycerol polyglycidyl ether poly(meth) acrylate Compound; 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, ethylene oxide bisphenol A Di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerin (meth) acrylate, neopentyl alcohol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, Crosslinkability of two polymerizable unsaturated groups in the molecule, such as diglycidyl phthalate di(meth) acrylate, hydroxytrimethyl acetic acid neopentyl diol di(meth) acrylate a compound; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl ( Methyl) acrylate, 2-(methyl) propylene oxy-2-hydroxypropyl ester, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2- A crosslinkable compound having one polymerizable unsaturated group in the molecule, such as (meth)acryloxyethyl phosphate or N-methylol (meth) acrylamide.

進而亦可使用下述式[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係表示選自由環己烷環、雙環己烷環、苯環、聯苯環、聯三苯環、萘環、茀環、蔥環及菲環所成群之基，E2係表示選自由下述式[7a]及式[7b]之基，n係表示1~4的整數) (In the formula [7A], E 1 represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, an onion ring, and a phenanthrene ring. group, E 2 represents a system selected from the following formulas [. 7A] and the formula [7B] of the group, n is an integer of 1 to line 4)

上述係交聯性化合物之一例，並非被限定於此等中。又，使用於本發明之液晶配向劑之交聯性化合物係可以1 種類、或可組合2種類以上。 An example of the above-mentioned crosslinkable compound is not limited thereto. Further, the crosslinkable compound used in the liquid crystal alignment agent of the present invention may be 1 Two or more types can be combined.

於本發明之液晶配向劑中，交聯性化合物之含有量相對於所有的聚合物成分100質量份，以0.1~150質量份為較佳。其中，為了進行交聯反應且展現目的之效果，相對於所有的聚合物成分100質量份，以0.1~100質量份為較佳。又較佳者為1~50質量份。 In the liquid crystal alignment agent of the present invention, the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass based on 100 parts by mass of all the polymer components. Among them, the effect of exhibiting the crosslinking reaction in order to carry out the crosslinking reaction is preferably 0.1 to 100 parts by mass based on 100 parts by mass of all the polymer components. Further preferably, it is 1 to 50 parts by mass.

本發明之液晶配向劑只要不損及本發明之效果內，可使用使塗佈液晶配向劑時之液晶配向膜的膜厚之均勻性或表面平滑性提昇之化合物。 The liquid crystal alignment agent of the present invention can be used as long as it does not impair the effects of the present invention, and can improve the uniformity of the film thickness or the surface smoothness of the liquid crystal alignment film when the liquid crystal alignment agent is applied.

作為使液晶配向膜的膜厚之均勻性或表面平滑性提昇之化合物，可舉例氟系界面活性劑、聚矽氧系界面活性劑、非離子系界面活性劑等。 A fluorine-based surfactant, a polyfluorene-based surfactant, a nonionic surfactant, or the like can be exemplified as a compound which improves the uniformity of the film thickness of the liquid crystal alignment film or the surface smoothness.

更具體而言，可舉例如F-Top EF301、EF303、EF352(以上Tochem Products公司製)、MEGAFACE F171、F173、R-30(以上大日本油墨公司製)、Fluorad FC430、FC431(以上住友3M公司製)、AashiGuard AG710、Surflon 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 (manufactured by Tochem Products Co., Ltd.), MEGAFACE F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, and FC431 (above Sumitomo 3M) System, AashiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.).

界面活性劑之使用量，相對於液晶配向劑中所含有之所有的聚合物成分100質量份，為較佳0.01~2質量份，又較佳為0.01~1質量份。 The amount of the surfactant to be used is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.

進而，於液晶配向劑中，作為促進液晶配向膜中之電荷移動並促進元件的電荷釋放之化合物，亦可添加國際公開公報WO2011/132751號(2011.10.27公開) 的69~73頁所揭示之式[M1]~式[M156]所表示之含氮之雜環胺化合物。此胺化合物係亦可直接添加於液晶配向劑中濃度為0.1~10質量%，較佳以成為1~7質量%的溶液後來作添加為較佳。此溶劑只要可將特定聚合物(A)溶解即可無特別限定。 Further, in the liquid crystal alignment agent, as a compound which promotes charge transfer in the liquid crystal alignment film and promotes charge release of the element, International Publication WO2011/132751 (published 2011.10.27) may be added. The nitrogen-containing heterocyclic amine compound represented by the formula [M1]~[M156] disclosed on pages 69 to 73. The amine compound may be added directly to the liquid crystal alignment agent at a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass, and then preferably added. This solvent is not particularly limited as long as it can dissolve the specific polymer (A).

於本發明之液晶配向劑中，除了上述不良溶劑、交聯性化合物、樹脂被膜或使液晶配向膜的膜厚之均勻性或表面平滑性提昇之化合物及促進電荷釋放之化合物以外，只要不損及本發明之效果的範圍內，亦可添加以使液晶配向膜之介電率或導電性等的電特性變化為目的的介電質或導電物質。 In the liquid crystal alignment agent of the present invention, the poor solvent, the crosslinkable compound, the resin film or the compound which improves the uniformity of the film thickness or the surface smoothness of the liquid crystal alignment film and the compound which promotes charge release are not damaged. In addition, in the range of the effects of the present invention, a dielectric or a conductive material for changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film may be added.

<液晶配向膜‧液晶顯示元件> <Liquid alignment film ‧ Liquid crystal display element>

液晶配向膜係將上述液晶配向劑塗佈於基板上、乾燥並燒成後所得的膜。作為塗佈本發明之液晶配向劑之基板，只要是透明性高的基板即可無特別限定，玻璃基板、氮化矽基板，同時亦可使用丙烯酸板或聚碳酸酯基板等的塑膠基板等。此時，若使用形成有用來驅動液晶的ITO電極等的基板時，就製程的簡化之點而言為較佳。又，反射型之液晶顯示元件中，若僅單側之基板，則亦可使用矽晶圓等的不透明物，此時的電極亦可使用鋁等的會反射光的材料。 The liquid crystal alignment film is a film obtained by applying the above liquid crystal alignment agent onto a substrate, drying, and baking. 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 glass substrate or a tantalum nitride substrate may be a plastic substrate such as an acrylic plate or a polycarbonate 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 in terms of simplification of the process. Further, in the reflective liquid crystal display device, an opaque material such as a germanium wafer may be used as the substrate on only one side, and a material such as aluminum that reflects light may be used as the electrode.

液晶配向劑之塗佈方法係無特別限定，工業上而言，以網板印刷、平板印刷、柔版印刷、噴墨法等所 進行的方法為一般的。作為其他的塗佈方法係有浸漬法、輥塗佈法、縫塗佈法、旋轉器法、噴霧法等，因應目的亦可使用此等。 The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, screen printing, lithography, flexographic printing, and inkjet printing are used. The method performed is general. Other coating methods include a dipping method, a roll coating method, a slit coating method, a spinner method, a spray method, and the like, and these may be used depending on the purpose.

將液晶配向劑塗佈於基板上後，係藉由加熱板、熱循環型烘箱、IR(紅外線)型烘箱等的加熱方法，可使溶劑蒸發後來作成為液晶配向膜。塗佈本發明之液晶配向劑後的乾燥、燒成步驟，係可選擇任意的溫度與時間。一般而言為了充分地除去所含有的溶劑，可舉例以50~120℃，較佳為以60~100℃下、1~10分鐘，較佳為乾燥1~5分鐘，之後以150~300℃，較佳為以180~250℃下、5~120分鐘，較佳為10~60分鐘來進行燒成之條件。燒成後的液晶配向膜的厚度，若過薄時有降低液晶顯示元件之可靠性之情形，故以5~300nm為較佳，10~200nm為又較佳。 After the liquid crystal alignment agent is applied onto the substrate, the solvent is evaporated by a heating method such as a hot plate, a heat cycle type oven, or an IR (infrared) type oven to form a liquid crystal alignment film. 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. In general, in order to sufficiently remove the solvent contained, it may be, for example, 50 to 120 ° C, preferably 60 to 100 ° C, 1 to 10 minutes, preferably 1 to 5 minutes, and then 150 to 300 ° C. Preferably, the firing is carried out at 180 to 250 ° C for 5 to 120 minutes, preferably 10 to 60 minutes. The thickness of the liquid crystal alignment film after firing is preferably reduced to 5 to 300 nm, and preferably 10 to 200 nm, if the thickness of the liquid crystal alignment film is too thin.

將由本發明之液晶配向劑所得的液晶配向膜進行配向處理之方法係可以用摩擦處理法，但以光配向處理法為合適。作為光配向處理法之較佳的例子，係可舉例於前述液晶配向膜的表面上，照射朝一定方向所偏向的放射線，依情形較佳為以用150~250℃的溫度進行加熱處理，賦予液晶配向性(亦稱為液晶配向能)之方法。作為放射線係可使用具有100~800nm的波長之紫外線或可視光線。其中，較佳為100~400nm，又較佳為具有200~400nm的波長之紫外線。 The method of performing the alignment treatment on the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention may be a rubbing treatment method, but a photoalignment treatment method is suitable. A preferred example of the photo-alignment treatment method is exemplified by irradiating radiation on a surface of the liquid crystal alignment film in a certain direction, and heating is preferably performed at a temperature of 150 to 250 ° C depending on the case. A method of liquid crystal alignment (also referred to as liquid crystal alignment). As the radiation system, ultraviolet rays or visible light having a wavelength of 100 to 800 nm can be used. Among them, it is preferably 100 to 400 nm, and more preferably ultraviolet light having a wavelength of 200 to 400 nm.

又，為了改善液晶配向性，將塗膜液晶配向膜的基板以50~250℃進行加熱，同時亦可照射放射線。 Further, in order to improve the liquid crystal alignment property, the substrate of the coating liquid crystal alignment film is heated at 50 to 250 ° C, and radiation may be irradiated.

前述放射線之照射量係以1~10,000mJ/cm2為較佳。其中，以100~5,000mJ/cm2為較佳。以如此般的方式所製作的液晶配向膜係可將液晶分子朝一定的方向來作安定後使其配向。 The irradiation amount of the radiation is preferably 1 to 10,000 mJ/cm 2 . Among them, 100 to 5,000 mJ/cm 2 is preferred. The liquid crystal alignment film produced in such a manner can stabilize the liquid crystal molecules in a certain direction and then align them.

進而，採前述方法使用水或溶劑來與照射經偏光的放射線的液晶配向膜進行接觸處理。 Further, the above method uses water or a solvent to perform a contact treatment with a liquid crystal alignment film that irradiates the polarized radiation.

作為使用於上述接觸處理之溶劑，只要能溶解藉由放射線的照射而由液晶配向膜所生成的分解物的溶劑即可無特別限定。作為具體例，可舉例水、甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮、1-甲氧基-2-丙醇、1-甲氧基-2-丙醇乙酸酯、丁基賽璐蘇、乳酸乙酯、乳酸甲酯、二丙酮醇、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸環己酯等。其中，就泛用性或溶劑的安全性之點而言，以水、2-丙醇、1-甲氧基-2-丙醇或乳酸乙酯為較佳。又較佳者為水、1-甲氧基-2-丙醇或乳酸乙酯。溶劑係可以1種類、或可組合2種類以上。 The solvent to be used in the above-described contact treatment is not particularly limited as long as it can dissolve the decomposition product generated by the liquid crystal alignment film by irradiation of radiation. Specific examples thereof include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, and 1-methoxy-2-propanol acetate. Butyl cyproterone, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate Wait. Among them, water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate is preferred in terms of generality or safety of the solvent. Still more preferred is water, 1-methoxy-2-propanol or ethyl lactate. The solvent may be one type or two or more types.

作為上述接觸處理，可舉例浸漬處理或噴霧處理(亦稱為噴霧處理)。於此等的處理之處理時間，就有效率地溶解藉由放射線而由液晶配向膜所生成的分解物之點而言，以10秒鐘~1小時為較佳。其中，以進行1~30分鐘浸漬處理為較佳。又，前述接觸處理時的溶劑可常溫亦可加溫，但較佳為10~80℃。其中，以20~50℃為較佳。另外，就分解物之溶解性之點而言，因應所需亦可進行超音波處理等。 As the above contact treatment, an immersion treatment or a spray treatment (also referred to as a spray treatment) can be exemplified. The treatment time of these treatments is preferably from 10 seconds to 1 hour in order to efficiently dissolve the decomposition product generated by the liquid crystal alignment film by radiation. Among them, it is preferred to carry out the immersion treatment for 1 to 30 minutes. Further, the solvent during the contact treatment may be heated at normal temperature, but is preferably from 10 to 80 °C. Among them, 20 to 50 ° C is preferred. Further, in terms of the solubility of the decomposition product, ultrasonic treatment or the like may be performed as needed.

於前述接觸處理後，以藉由水、甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮等的低沸點溶劑之洗滌(亦稱為潤濕)或進行液晶配向膜之燒成為較佳。此時，可進行潤濕與燒成任何一種、或亦可進行兩者。燒成的溫度係以150~300℃為較佳。其中，以180~250℃為較佳。又較佳者為200~230℃。又，燒成的時間係以10秒鐘~30分鐘為較佳。其中，以1~10分鐘為較佳。 After the above contact treatment, washing with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone (also referred to as wetting) or burning of the liquid crystal alignment film becomes good. At this time, any one of wetting and baking may be performed, or both may be performed. The firing temperature is preferably 150 to 300 °C. Among them, 180 to 250 ° C is preferred. More preferably, it is 200 to 230 °C. Further, the firing time is preferably from 10 seconds to 30 minutes. Among them, 1 to 10 minutes is preferred.

本發明之液晶配向膜係適合作為IPS方式或FFS方式等的橫向電場方式的液晶顯示元件之液晶配向膜，特別是有利於作為FFS方式的液晶顯示元件之液晶配向膜。液晶顯示元件係得到附有由本發明之液晶配向劑所得的液晶配向膜的基板後，以習知的方法來製作液晶晶胞，且使用該液晶晶胞而得。 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 transverse electric field type such as an IPS method or an FFS method, and is particularly advantageous as a liquid crystal alignment film of an FFS type liquid crystal display element. In the liquid crystal display device, a substrate having a liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention is obtained, and a liquid crystal cell is produced by a known method, and the liquid crystal cell is used.

作為液晶晶胞之製作方法之一例子，藉由例子來說明被動矩陣構造的液晶顯示元件。尚，亦可以是在構成畫面顯示之各畫素部分，設置有TFT(Thin Film Transistor)等的開關元件之主動矩陣構造的液晶顯示元件。 As an example of a method of fabricating a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described by way of example. In addition, a liquid crystal display element having an active matrix structure of a switching element such as a TFT (Thin Film Transistor) may be provided in each pixel portion constituting the screen display.

具體而言，準備透明的玻璃製的基板，於一片基板之上設置共用(common)電極，另一片基板之上設置節段(segment)電極。此等的電極係可以例如ITO電極，形成為能呈現所期望畫面顯示的圖型化。接著，於各基板之上以被覆共用(common)電極與節段(segment)電極之方式來設置絕緣膜。絕緣膜係可作成為藉由例如溶膠-凝膠法所形成的SiO2-TiO2膜。 Specifically, a transparent glass substrate is prepared, and a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate. Such electrode systems can be formed, for example, as ITO electrodes, to provide a patterning of the desired picture display. Next, an insulating film is provided on each of the substrates so as to cover the common electrode and the segment electrode. The insulating film can be used as a SiO 2 -TiO 2 film formed by, for example, a sol-gel method.

接著，於各基板之上形成液晶配向膜，將另一片基板以彼此的液晶配向膜面呈對向之方式來重疊另一片基板，並用密封劑來接著周邊。對於密封劑，為了控制基板間隙，一般先混入間隔物，又即使是未設置密封劑的面內部分，亦以先散布基板間隙控制用的間隔物為較佳。於密封劑的一部份先設置由外部可填充液晶的開口部。接著，通過設置於密封劑的開口部，向以2片基板與密封劑所包圍的空間內注入液晶材料，之後，用接著劑密封此開口部。對於注入可使用真空注入法、亦可使用在大氣中利用毛細管現象之方法。液晶材料係亦可使用正型液晶材料或負型液晶材料中任一者，較佳者為負型液晶材料。接著，進行偏光板的設置。具體而言，在2片基板的液晶層與相反側的面上黏貼一對偏光板。 Next, a liquid crystal alignment film is formed on each of the substrates, and the other substrate is superposed on the other substrate so that the liquid crystal alignment film faces face each other, and the periphery is surrounded by a sealant. In order to control the gap of the substrate, the spacer is generally mixed with the spacer first, and even if the in-plane portion is not provided with the sealant, it is preferable to disperse the spacer for controlling the gap of the substrate first. A portion of the encapsulant is provided with an opening portion which can be filled with an external liquid. Next, the liquid crystal material is injected into the space surrounded by the two substrates and the sealant by the opening provided in the sealant, and then the opening is sealed with an adhesive. For the injection, a vacuum injection method or a method of utilizing a capillary phenomenon in the atmosphere can be used. The liquid crystal material may also be any of a positive liquid crystal material or a negative liquid crystal material, preferably a negative liquid crystal material. Next, the setting of the polarizing plate is performed. Specifically, a pair of polarizing plates are adhered to the liquid crystal layer of the two substrates and the surface on the opposite side.

以如上述般之方式，藉由使用本發明之液晶配向劑，不但抑制因交流驅動而引起的殘影，且可得到兼具密封劑及底層基板之密著性之液晶配向膜。特別是對於照射經偏光的放射線後所得的光配向處理法用的液晶配向膜為有利。 By using the liquid crystal alignment agent of the present invention as described above, not only the image sticking due to the AC driving but also the liquid crystal alignment film having the adhesion between the sealant and the underlying substrate can be obtained. In particular, it is advantageous for a liquid crystal alignment film for a photo-alignment treatment method obtained by irradiating a polarized radiation.

[實施例] [Examples]

以下將舉出實施例更詳細地說明本發明，但本發明並不限定於該等。以下中所使用的化合物代號、及各特性之測定方法係如下述般。 Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. The compound code used in the following and the measurement method of each characteristic are as follows.

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

BCS：丁基賽璐蘇 BCS: Butyl cypress

DA-1：1,2-雙(4-胺基苯氧基)乙烷 DA-1:1,2-bis(4-aminophenoxy)ethane

DA-2：4-(2-(甲基胺基)乙基)苯胺 DA-2: 4-(2-(methylamino)ethyl)aniline

DA-3：p-苯二胺 DA-3: p-phenylenediamine

DA-4：4-(2-胺基乙基)苯胺 DA-4: 4-(2-Aminoethyl)aniline

DA-5：參考下述式(DA-5) DA-5: Refer to the following formula (DA-5)

[黏度] [viscosity]

聚醯胺酸酯及聚醯胺酸溶液等的黏度，係使用E型黏度計TVE-22H(東機產業公司製)，以樣品量1.1mL、錐形轉子TE-1(1°34’、R24)、溫度25℃之條件下進行測定。 For the viscosity of the polyglycolate and the polyaminic acid solution, an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) was used, and the sample amount was 1.1 mL, and the cone rotor TE-1 (1° 34', R24) and measurement at a temperature of 25 °C.

[分子量] [molecular weight]

聚醯胺酸酯等的分子量，係藉由GPC(常溫凝膠滲透 層析法)裝置來進行測定，以作為聚乙二醇及聚環氧乙烷換算值來算出數平均分子量(Mn)與重量平均分子量(Mw)。 The molecular weight of polyperurethane or the like is by GPC (normal temperature gel penetration) The apparatus was measured by a chromatography method to calculate a number average molecular weight (Mn) and a weight average molecular weight (Mw) as polyethylene glycol and polyethylene oxide equivalent values.

GPC裝置：Shodex公司製(GPC-101)、管柱：Shodex公司製(KD803、KD805之串連)、管柱溫度：50℃、溶離液：N,N-二甲基甲醯胺(添加劑為溴化鋰-水和物(LiBr‧H2O)30mmol/L、磷酸‧無水結晶(o-磷酸)為30mmol/L、四氫呋喃(THF)為10ml/L)、流速：1.0ml/分 GPC device: manufactured by Shodex Co., Ltd. (GPC-101), pipe column: manufactured by Shodex Co., Ltd. (KD803, KD805 series), column temperature: 50 ° C, dissolving solution: N, N-dimethylformamide (additive Lithium bromide-water and (LiBr‧H 2 O) 30 mmol/L, phosphoric acid ‧ anhydrous crystals (o-phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) 10 ml/L), flow rate: 1.0 ml/min

檢量線製作用標準樣品：Tosoh公司製TSK標準聚環氧乙烷(重量平均分子量(Mw)約900,000、150,000、100,000、30,000)、及Polymer Laboratory公司製聚乙二醇(峰頂分子量(Mp)約12,000、4,000、1,000)。測定時為了避免波峰重疊，係各別測定混合900,000、100,000、12,000、1,000之4種所得的樣品、及混合150,000、30,000、4,000之3種所得的樣品之2種樣品。 Standard sample for the production of calibration lines: TSK standard polyethylene oxide manufactured by Tosoh Co., Ltd. (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30,000), and polyethylene glycol manufactured by Polymer Laboratory (peak weight (Mp) ) about 12,000, 4,000, 1,000). In order to avoid overlapping of peaks in the measurement, two kinds of samples obtained by mixing four kinds of samples of 900,000, 100,000, 12,000, and 1,000, and two kinds of samples obtained by mixing three types of 150,000, 30,000, and 4,000 were separately measured.

[配向膜之異向性] [Anisotropy of alignment film]

使用Moritex公司製之液晶配向膜評估系統「LayScan-Labo H」(LYS-LH30S-1A)來進行測定。介隔著偏光板對於膜厚100nm的聚醯亞胺膜照射以消光比10：1以上的直線偏光之波長254nm的紫外線，來測定相對於所得的配向膜之配向方向之異向性的大小。 The measurement was carried out using a liquid crystal alignment film evaluation system "LayScan-Labo H" (LYS-LH30S-1A) manufactured by Moritex. The polyimine film having a thickness of 100 nm was irradiated with ultraviolet rays having a wavelength of 254 nm at a linear extinction ratio of 10:1 or more with a polarizing plate interposed therebetween, and the anisotropy of the alignment direction with respect to the obtained alignment film was measured.

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

製作具備有邊緣場開關(Fringe Field Switching：FFS)模式液晶顯示元件之構成之液晶晶胞。 A liquid crystal cell having a structure of a Fringe Field Switching (FFS) mode liquid crystal display element was fabricated.

首先，準備附有電極的基板。基板係以30mm×50mm之大小、厚度為0.7mm的玻璃基板。在基板上係形成有作為第1層之構成對向電極的具備有整體狀圖案(solid pattern)的ITO電極。於第1層的對向電極之上係形成有作為第2層之藉由CVD法所成膜的SiN(氮化矽)膜。第2層的SiN膜的膜厚為500nm，以作為層間絕緣膜來發揮功能。於第2層的SiN膜之上，配置作為第3層之使ITO膜圖型化所形成的梳齒狀之畫素電極，而形成第1畫素及第2畫素之2個畫素。各畫素之尺寸係長10mm且寬約5mm。此時，第1層之對向電極與第3層之畫素電極，係因第2層的SiN膜之作用而電性絕緣。 First, a substrate to which an electrode is attached is prepared. The substrate was a glass substrate having a size of 30 mm × 50 mm and a thickness of 0.7 mm. An ITO electrode having a solid pattern as a counter electrode constituting the first layer is formed on the substrate. An SiN (tantalum nitride) film formed as a second layer by a CVD method is formed on the counter electrode of the first layer. The SiN film of the second layer has a film thickness of 500 nm and functions as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning an ITO film as a third layer is disposed to form two pixels of the first pixel and the second pixel. The dimensions of each pixel are 10 mm long and about 5 mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

第3層之畫素電極係具有配列多個中央部分撓曲的「ㄑ字」形狀的電極要素所構成的梳齒狀形狀。各電極要素之短邊方向的寬為3μm，電極要素間之間隔為6μm。形成各畫素之畫素電極，因為配列多個中央部分撓曲的ㄑ字形狀的電極要素所構成，故各畫素的形狀並非長方形狀，而係具備有與電極要素相同地中央部分撓曲的、類似粗字體的ㄑ字之形狀。又，各畫素係以其中央的撓曲部分為界來上下分割，而具有撓曲部分之上側的第1區域與下側的第2區域。 The third layer of the pixel electrode has a comb-tooth shape in which a plurality of electrode elements having a "ㄑ" shape in which a plurality of central portions are bent are arranged. The width of each electrode element in the short-side direction was 3 μm, and the interval between the electrode elements was 6 μm. The pixel electrodes forming the respective pixels are formed by arranging a plurality of electrode elements having a U-shaped shape in which the central portion is bent. Therefore, the shape of each pixel is not a rectangular shape, but the central portion is deflected in the same manner as the electrode elements. The shape of a lyrics similar to a bold font. Further, each of the pixels is vertically divided by a central portion of the curved portion, and has a first region on the upper side of the flexure portion and a second region on the lower side.

若比較各畫素的第1區域與第2區域時，構成該等的畫素電極的電極要素之形成方向係呈相異者。即，若以後述之液晶配向膜之摩擦方向為基準時，於畫素的第1區域中，畫素電極之電極要素係以呈+10°之角度(順時計)之方式來形成，於畫素的第2區域中，畫素電極之電極要素係以呈-10°之角度(順時計)之方式來形成。即，於各畫素的第1區域與第2區域中，藉由畫素電極與對向電極之間的電壓外加所誘發的液晶，於基板面內的旋轉動作(平面內切換)之方向係以彼此互相呈反方向之方式來構成。 When the first region and the second region of each pixel are compared, the direction in which the electrode elements constituting the pixel elements are formed is different. In other words, when the rubbing direction of the liquid crystal alignment film to be described later is used as a reference, in the first region of the pixel, the electrode elements of the pixel electrode are formed at an angle of +10° (in time). In the second region of the element, the electrode elements of the pixel electrode are formed at an angle of -10° (in time). In other words, in the first region and the second region of each pixel, the liquid crystal induced by the voltage between the pixel electrode and the counter electrode is applied to the direction of rotation (in-plane switching) in the plane of the substrate. They are constructed in such a way that they are opposite to each other.

接著，用1.0μm的過濾器將液晶配向劑過濾後，於已準備的上述附有電極之基板與背面成膜有ITO膜之具有高度4μm的柱狀間隔物之玻璃基板上，予以旋轉塗佈來進行塗佈。於80℃的加熱板上使其乾燥5分鐘後，用230℃的熱風循環式烘箱進行20分鐘燒成來形成膜厚100nm的塗膜。介隔著偏光板對於此塗膜面照射以消光比10：1以上的直線偏光之波長254nm的紫外線。將此基板浸漬於選自由水及有機溶劑中之至少1種的溶劑3分鐘，接著，浸漬於純水1分鐘，於150~300℃的加熱板上加熱5分鐘，可得到附有液晶配向膜之基板。以上述2片基板為一組，於基板上印刷密封劑，將另1片基板以液晶配向膜面互為對向且配向方向成為0°之方式來貼合後，使密封劑硬化製作空晶胞。對於此空晶胞藉由減壓注入法注入液晶MLC-7026-100(Merck公司製)，並將注 入口密封後可得到FFS驅動液晶晶胞。之後，將所得的液晶晶胞以110℃加熱1小時，放置一晚後使用於各評估中。 Subsequently, the liquid crystal alignment agent was filtered through a 1.0 μm filter, and then spin-coated on the prepared electrode substrate and the glass substrate having a columnar spacer having a height of 4 μm on the back surface of which an ITO film was formed. To apply. After drying on a hot plate at 80 ° C for 5 minutes, the film was fired in a hot air circulating oven at 230 ° C for 20 minutes to form a coating film having a thickness of 100 nm. The coating film surface was irradiated with ultraviolet rays having a wavelength of 254 nm of a linearly polarized light having an extinction ratio of 10:1 or more across the polarizing plate. The substrate is immersed in a solvent selected from at least one of water and an organic solvent for 3 minutes, and then immersed in pure water for 1 minute, and heated on a hot plate at 150 to 300 ° C for 5 minutes to obtain a liquid crystal alignment film. The substrate. The sealant is printed on the substrate by using the two substrates as one set, and the other substrate is bonded so that the liquid crystal alignment film faces are opposite to each other and the alignment direction is 0°, and then the sealant is hardened to form an air crystal. Cell. For this empty cell, liquid crystal MLC-7026-100 (manufactured by Merck) was injected by a vacuum injection method, and the injection was performed. The FFS drive liquid crystal cell can be obtained after the inlet is sealed. Thereafter, the obtained liquid crystal cell was heated at 110 ° C for 1 hour, and left for one night and used in each evaluation.

[長期交流驅動之殘影評估] [Research on the residual image of long-term AC drive]

準備與使用於上述之殘影評估的液晶晶胞為相同構造之液晶晶胞。 A liquid crystal cell of the same configuration as that of the liquid crystal cell used for the above-described afterimage evaluation is prepared.

使用此液晶晶胞，在60℃的恆溫環境下，外加以周波數60Hz±5V的交流電壓120小時。之後，使液晶晶胞的畫素電極與對向電極之間成為短路狀態，直接於室溫放置一日。 Using this liquid crystal cell, an alternating voltage of 60 Hz ± 5 V was applied for 120 hours in a constant temperature environment of 60 ° C. Thereafter, the pixel electrode of the liquid crystal cell and the counter electrode were brought into a short-circuit state, and were allowed to stand at room temperature for one day.

放置後，將液晶晶胞配置於為偏光軸正交的2片偏光板之間，於無外加電壓之狀態下將背光預先點燈，將液晶晶胞的配置角度調整為透過光之輝度成為最小。又，算出將液晶晶胞由第1畫素的第2區域為最暗的角度起旋轉至第1區域為最暗的角度為止時的旋轉角度作為角度△。第2畫素亦相同地，比較第2區域與第1區域，算出相同的角度△。又，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△，以其值之大小評估液晶配向性。即，此角度△的值越小則液晶配向性為良好。 After being placed, the liquid crystal cell is disposed between two polarizing plates having orthogonal polarization axes, and the backlight is pre-lighted without an applied voltage, and the arrangement angle of the liquid crystal cell is adjusted to minimize the luminance of the transmitted light. . Further, the rotation angle when the liquid crystal cell is rotated from the angle at which the second region of the first pixel is the darkest to the angle at which the first region is the darkest is calculated as the angle Δ. Similarly to the second pixel, the second region and the first region are compared, and the same angle Δ is calculated. Further, the average value of the angle Δ values of the first pixel and the second pixel was calculated as the angle Δ of the liquid crystal cell, and the liquid crystal alignment property was evaluated by the magnitude of the value. That is, the smaller the value of the angle Δ is, the better the liquid crystal alignment property is.

[液晶晶胞的輝點之評估(對比)] [Evaluation of the bright spot of liquid crystal cell (comparative)]

進行與上述(液晶晶胞之製作)相同地製作之液晶晶胞的輝點之評估。 Evaluation of the bright spot of the liquid crystal cell produced in the same manner as described above (manufacture of liquid crystal cell) was performed.

藉由用偏光顯微鏡(ECLIPSE E600WPOL)(Nikon公司製)觀察液晶晶胞來進行。具體而言，係將液晶晶胞以正交尼科耳來設置，以倍率設為5倍之偏光顯微鏡來觀察液晶晶胞，計數所確認的輝點之數目，若輝點的數目未滿10個為「良好」、以該值以上為「不良」。 This was carried out by observing a liquid crystal cell with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation). Specifically, the liquid crystal cell is arranged in crossed Nicols, and the liquid crystal cell is observed by a polarizing microscope having a magnification of 5 times, and the number of confirmed bright spots is counted, and if the number of bright spots is less than 10 The number is "good" and the value is "bad".

<合成例1> <Synthesis Example 1>

在附有攪拌裝置及附有氮導入管的50mL四頸燒瓶中，量取DA-1 1.03g(4.20mmol)、DA-2 0.421g(2.80mmol)、DA-3 0.76g(7.00mmol)，並加入NMP 33.60g後，一邊送入氮一邊攪拌使其溶解。一邊攪拌該二胺溶液，一邊添加1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐2.95g(13.16mmol)，進而加入NMP 3.73g使固體成分濃度成為12質量%。之後，在室溫下攪拌24小時可得到聚醯胺酸溶液(A)。該聚醯胺酸溶液於溫度25℃之黏度為316mPa‧s。又，該聚醯胺酸之分子量為Mn=13530、Mw=29850。 In a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-1 1.03 g (4.20 mmol), DA-2 0.421 g (2.80 mmol), and DA-3 0.76 g (7.00 mmol) were weighed. After adding 33.60 g of NMP, it was stirred and dissolved while feeding nitrogen. While stirring the diamine solution, 2.95 g (13.16 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and 3.73 g of NMP was further added to adjust the solid content concentration. 12% by mass. Thereafter, the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (A). The polyamic acid solution has a viscosity of 316 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 13530 and Mw = 29850.

<合成例2> <Synthesis Example 2>

在附有攪拌裝置及附有氮導入管的50mL四頸燒瓶中，量取DA-1 0.95g(3.90mmol)、DA-2 0.98g(6.5mmol)、DA-4 0.35g(2.60mmol)，並加入NMP 33.15g後，一邊送入氮一邊攪拌使其溶解。一邊攪拌該二胺溶液，一邊添加1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐 2.74g(12.22mmol)，進而加入NMP 3.73g使固體成分濃度成為12質量%。之後，在室溫下攪拌24小時可得到聚醯胺酸溶液(B)。該聚醯胺酸溶液於溫度25℃之黏度為483mPa‧s。又，該聚醯胺酸之分子量為Mn=14260、Mw=30050。 In a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-1 0.95 g (3.90 mmol), DA-2 0.98 g (6.5 mmol), and DA-4 0.35 g (2.60 mmol) were weighed. After adding 33.15 g of NMP, it was stirred and dissolved while feeding nitrogen. Adding 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride while stirring the diamine solution 2.74 g (12.22 mmol) was further added to 3.73 g of NMP so that the solid content concentration became 12% by mass. Thereafter, the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (B). The polyamic acid solution had a viscosity of 483 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 14260 and Mw = 30050.

<合成例3> <Synthesis Example 3>

在附有攪拌裝置及附有氮導入管的50mL四頸燒瓶中，量取DA-1 1.47g(6.00mmol)、DA-2 0.90g(6.00mmol)，並加入NMP 31.96g後，一邊送入氮一邊攪拌使其溶解。一邊攪拌該二胺溶液，一邊添加1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐2.60g(11.58mmol)，進而加入NMP 3.55g使固體成分濃度成為12質量%。之後，在室溫下攪拌24小時可得到聚醯胺酸溶液(C)。該聚醯胺酸溶液於溫度25℃之黏度為423mPa‧s。又，該聚醯胺酸之分子量為Mn=14010、Mw=29540。 In a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-1 1.47 g (6.00 mmol) and DA-2 0.90 g (6.00 mmol) were weighed, and after adding NMP 31.96 g, it was fed. The nitrogen is dissolved while stirring. While stirring the diamine solution, 2.60 g (11.58 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and further, NMP 3.55 g was added to adjust the solid content concentration. 12% by mass. Thereafter, the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (C). The polyamic acid solution had a viscosity of 423 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 14010 and Mw = 29540.

<合成例4> <Synthesis Example 4>

在附有攪拌裝置及附有氮導入管的50mL四頸燒瓶中，量取DA-1 1.59g(6.50mmol)、DA-3 0.70g(6.50mmol)，並加入NMP 33.01g後，一邊送入氮一邊攪拌使其溶解。一邊攪拌該二胺溶液，一邊添加1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐2.78g(12.42mmol)，進而加入NMP 3.66g使固體成分濃度成為12質量%。之後， 在室溫下攪拌24小時可得到聚醯胺酸溶液(D)。該聚醯胺酸溶液於溫度25℃之黏度為360mPa‧s。又，該聚醯胺酸之分子量為Mn=13810、Mw=28400。 In a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-1 1.59 g (6.50 mmol) and DA-3 0.70 g (6.50 mmol) were weighed, and after adding NMP 33.01 g, it was fed. The nitrogen is dissolved while stirring. 2.7% (1,3-. 12% by mass. after that, The polyglycine solution (D) was obtained by stirring at room temperature for 24 hours. The polyamic acid solution has a viscosity of 360 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 13810 and Mw = 28,400.

<合成例5> <Synthesis Example 5>

在附有攪拌裝置及附有氮導入管的50mL四頸燒瓶中，量取DA-1 1.03g(4.20mmol)、DA-3 0.76g(7.00mmol)、DA-4 0.38g(2.80mmol)，並加入NMP 34.38g，一邊送入氮一邊攪拌使其溶解。一邊攪拌該二胺溶液，一邊添加1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐3.04g(13.58mmol)，進而加入NMP 3.82g使固體成分濃度成為12質量%。之後，在室溫下攪拌24小時可得到聚醯胺酸溶液(E)。該聚醯胺酸溶液於溫度25℃之黏度為428mPa‧s。又，該聚醯胺酸之分子量為Mn=14080、Mw=29960。 In a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-1 1.03 g (4.20 mmol), DA-3 0.76 g (7.00 mmol), and DA-4 0.38 g (2.80 mmol) were weighed. Further, 34.38 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring the diamine solution, 3.04 g (13.58 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and 3.82 g of NMP was further added to increase the solid content concentration. 12% by mass. Thereafter, the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (E). The polyamic acid solution had a viscosity of 428 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyamic acid was Mn = 14080 and Mw = 29,960.

<合成例6> <Synthesis Example 6>

在附有攪拌裝置及附有氮導入管的50mL四頸燒瓶中，量取DA-2 1.13g(7.50mmol)、DA-3 0.81g(7.50mmol)，並加入NMP 33.87g後，一邊送入氮一邊攪拌使其溶解。一邊攪拌該二胺溶液，一邊添加1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐3.39g(14.85mmol)，進而加入NMP 3.76g使固體成分濃度成為12質量%。之後，在室溫下攪拌24小時可得到聚醯胺酸溶液(F)。該聚醯 胺酸溶液於溫度25℃之黏度為280mPa‧s。又，該聚醯胺酸之分子量為Mn=12250、Mw=26550。 In a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-2 1.13 g (7.50 mmol) and DA-3 0.81 g (7.50 mmol) were weighed, and after adding NMP 33.87 g, it was fed. The nitrogen is dissolved while stirring. While stirring the diamine solution, 3.39 g (14.85 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and 3.76 g of NMP was further added to adjust the solid content concentration. 12% by mass. Thereafter, the mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (F). The gathering The viscosity of the amine acid solution at a temperature of 25 ° C was 280 mPa ‧ s. Further, the molecular weight of the poly-proline was Mn = 12,250 and Mw = 26,550.

<合成例7> <Synthesis Example 7>

在附有攪拌裝置及附有氮導入管的50mL四頸燒瓶中，量取1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐3.36g(15.00mmol)，並加入NMP 3.73g後，一邊送入氮一邊攪拌使其溶解。一邊攪拌該酸二酐溶液，一邊添加DA-3 1.13g(12.68mmol)、DA-5 0.81g(1.50mmol)，進而加入NMP 7.46g使固體成分濃度成為10質量%。之後，在室溫下攪拌24小時可得到聚醯胺酸溶液(G)。該聚醯胺酸溶液於溫度25℃之黏度為460mPa‧s。又，該聚醯胺酸之分子量為Mn=15020、Mw=33320。 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 3.36 g (15.00 mmol) was weighed in a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube. After adding 3.73 g of NMP, it was stirred and dissolved while feeding nitrogen. While stirring the acid dianhydride solution, 1.13 g (12.68 mmol) of DA-3 and 0.81 g (1.50 mmol) of DA-5 were added, and 7.46 g of NMP was further added so that the solid content concentration became 10 mass%. Thereafter, the polyglycine solution (G) was obtained by stirring at room temperature for 24 hours. The polyamic acid solution had a viscosity of 460 mPa ‧ at a temperature of 25 ° C. Further, the molecular weight of the polyproline was Mn = 15020 and Mw = 33320.

<實施例1> <Example 1>

將12質量%的聚醯胺酸溶液(A)15.00g量取至100ml三角燒瓶中，加入NMP9.00g、及BCS6.00g，於25℃混合8小時後可得到液晶配向劑(1)。於此液晶配向劑中並未發現混濁或析出等的異常，可確認為均勻的溶液。 The amount of 1% by mass of 12% by mass of the polyaminic acid solution (A) was placed in a 100 ml Erlenmeyer flask, and NMP 9.00 g and BCS 6.00 g were added, and the mixture was mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment agent (1). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that it was a uniform solution.

<實施例2> <Example 2>

除了使用12質量%的聚醯胺酸溶液(B)15.00g以外，與實施例1以相同方式實施後而得到液晶配向劑 (2)。於此液晶配向劑中並未發現混濁或析出等的異常，可確認為均勻的溶液。 A liquid crystal alignment agent was obtained in the same manner as in Example 1 except that 15.00 g of a 12 mass% polyamic acid solution (B) was used. (2). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that it was a uniform solution.

<實施例3> <Example 3>

除了使用12質量%的聚醯胺酸溶液(C)15.00g以外，與實施例1以相同方式實施後而得到液晶配向劑(3)。於此液晶配向劑中並未發現混濁或析出等的異常，可確認為均勻的溶液。 The liquid crystal alignment agent (3) was obtained in the same manner as in Example 1 except that 15.00 g of a 12% by mass polyamine acid solution (C) was used. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that it was a uniform solution.

<比較例1> <Comparative Example 1>

除了使用12質量%的聚醯胺酸溶液(D)15.00g以外，與實施例1以相同方式實施後而得到液晶配向劑(4)。於此液晶配向劑中並未發現混濁或析出等的異常，可確認為均勻的溶液。 A liquid crystal alignment agent (4) was obtained in the same manner as in Example 1 except that 15.00 g of a 12 mass% polyamic acid solution (D) was used. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that it was a uniform solution.

<比較例2> <Comparative Example 2>

除了使用12質量%的聚醯胺酸溶液(E)15.00g以外，與實施例1以相同方式實施後而得到液晶配向劑(5)。於此液晶配向劑中並未發現混濁或析出等的異常，可確認為均勻的溶液。 A liquid crystal alignment agent (5) was obtained in the same manner as in Example 1 except that 15.00 g of a 12 mass% polyamine acid solution (E) was used. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that it was a uniform solution.

<比較例3> <Comparative Example 3>

除了使用12質量%的聚醯胺酸溶液(F)15.00g以外，與實施例1以相同方式實施後而得到液晶配向劑 (6)。於此液晶配向劑中並未發現混濁或析出等的異常，可確認為均勻的溶液。 A liquid crystal alignment agent was obtained in the same manner as in Example 1 except that 15.00 g of a 12% by mass polyglycine solution (F) was used. (6). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that it was a uniform solution.

<比較例4> <Comparative Example 4>

除了使用12質量%的聚醯胺酸溶液(G)15.00g以外，與實施例1以相同方式實施後而得到液晶配向劑(7)。於此液晶配向劑中並未發現混濁或析出等的異常，可確認為均勻的溶液。 A liquid crystal alignment agent (7) was obtained in the same manner as in Example 1 except that 15.00 g of a 12 mass% polyamic acid solution (G) was used. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that it was a uniform solution.

(實施例5) (Example 5)

用1.0μm的過濾器將上述液晶配向劑(1)過濾後，在30mm×40mm的ITO基板上予以旋轉塗佈來進行塗佈。於80℃的加熱板上使其乾燥2分鐘後，用230℃的熱風循環式烘箱進行14分鐘燒成來形成膜厚100nm的塗膜。介隔著偏光板對於此塗膜面照射以消光比26：1的直線偏光之波長254nm的紫外線，而可得到液晶配向膜。 The liquid crystal alignment agent (1) was filtered through a 1.0 μm filter, and then applied by spin coating on a 30 mm × 40 mm ITO substrate. After drying on a hot plate at 80 ° C for 2 minutes, the film was fired in a hot air circulating oven at 230 ° C for 14 minutes to form a coating film having a thickness of 100 nm. The liquid crystal alignment film was obtained by irradiating the coating film with ultraviolet rays having a wavelength of 254 nm at a linear extinction ratio of 26:1 across the polarizing plate.

測定相對於所得的液晶配向膜之配向方向之異向性的高度。上述紫外線之照射量在200mJ/cm2之異向性值為3.39、在300mJ/cm2之異向性值為4.10、在400mJ/cm2之異向性值為3.26。異向性成為最高之上述紫外線之照射量係300mJ/cm2，作為在光配向處理下之最適當照射條件。 The height of the anisotropy in the alignment direction with respect to the obtained liquid crystal alignment film was measured. The amount of the ultraviolet rays irradiated at 200 mJ/cm 2 was 3.39, the anisotropy value at 300 mJ/cm 2 was 4.10, and the anisotropy value at 400 mJ/cm 2 was 3.26. The irradiation amount of the ultraviolet rays having the highest anisotropy is 300 mJ/cm 2 , which is the most suitable irradiation condition under the photoalignment treatment.

(實施例6) (Example 6)

除了使用上述液晶配向劑(2)以外，與實施例5以 相同方式實施後而得到液晶配向膜。測定相對於所得的液晶配向膜之配向方向之異向性的大小。上述紫外線之照射量在50mJ/cm2之異向性值為0.05、在100mJ/cm2之異向性值為0.61、在200mJ/cm2之異向性值為0.06。異向性成為最大之上述紫外線之照射量係100mJ/cm2，作為在光配向處理下之最適當照射條件。 A liquid crystal alignment film was obtained in the same manner as in Example 5 except that the above liquid crystal alignment agent (2) was used. The magnitude of the anisotropy in the alignment direction with respect to the obtained liquid crystal alignment film was measured. The amount of ultraviolet rays irradiated at 50 mJ/cm 2 was 0.05, the anisotropy value at 100 mJ/cm 2 was 0.61, and the anisotropy value at 200 mJ/cm 2 was 0.06. The irradiation amount of the ultraviolet rays having the largest anisotropy is 100 mJ/cm 2 , which is the most suitable irradiation condition under the photoalignment treatment.

(實施例7) (Example 7)

除了使用上述液晶配向劑(3)以外，與實施例5以相同方式實施後可到液晶配向膜。測定相對於所得的液晶配向膜之配向方向之異向性的大小。上述紫外線之照射量係在50mJ/cm2之異向性值為0.10、在100mJ/cm2之異向性值為0.92、在200mJ/cm2之異向性值為0.15。異向性成為最大之上述紫外線之照射量係100mJ/cm2，作為在光配向處理下之最適當照射條件。 The liquid crystal alignment film can be applied in the same manner as in Example 5 except that the above liquid crystal alignment agent (3) is used. The magnitude of the anisotropy in the alignment direction with respect to the obtained liquid crystal alignment film was measured. The ultraviolet irradiation amount was such that the anisotropy value at 50 mJ/cm 2 was 0.10, the anisotropy value at 100 mJ/cm 2 was 0.92, and the anisotropy value at 200 mJ/cm 2 was 0.15. The irradiation amount of the ultraviolet rays having the largest anisotropy is 100 mJ/cm 2 , which is the most suitable irradiation condition under the photoalignment treatment.

(比較例5) (Comparative Example 5)

除了使用上述液晶配向劑(4)以外，與實施例5以相同方式實施後而得到液晶配向膜。測定相對於所得的液晶配向膜之配向方向之異向性的大小。上述紫外線之照射量係在100mJ/cm2之異向性值為3.02、在200mJ/cm2之異向性值為5.37、在300mJ/cm2之異向性值為3.40。異向性成為最大之上述紫外線之照射量係200mJ/cm2，作為在光配向處理下之最適當照射條件。 A liquid crystal alignment film was obtained in the same manner as in Example 5 except that the above liquid crystal alignment agent (4) was used. The magnitude of the anisotropy in the alignment direction with respect to the obtained liquid crystal alignment film was measured. The ultraviolet irradiation amount is an anisotropy value of 3.0 m 2 at 100 mJ/cm 2 , an anisotropy value of 5.37 at 200 mJ/cm 2 , and an anisotropy value of 3.40 at 300 mJ/cm 2 . The irradiation amount of the ultraviolet rays which is the largest in the anisotropy is 200 mJ/cm 2 , which is the most suitable irradiation condition under the light alignment treatment.

(比較例6) (Comparative Example 6)

除了使用上述液晶配向劑(5)以外，與實施例5以相同方式實施後而得到液晶配向膜。測定相對於所得的液晶配向膜之配向方向之異向性的大小。上述紫外線之照射量係在200mJ/cm2之異向性值為4.28、在300mJ/cm2之異向性值為4.57、在400mJ/cm2之異向性值為3.03。異向性成為最大之上述紫外線之照射量係300mJ/cm2，作為在光配向處理下之最適當照射條件。 A liquid crystal alignment film was obtained in the same manner as in Example 5 except that the above liquid crystal alignment agent (5) was used. The magnitude of the anisotropy in the alignment direction with respect to the obtained liquid crystal alignment film was measured. The ultraviolet irradiation amount was such that the anisotropy value at 200 mJ/cm 2 was 4.28, the anisotropy value at 300 mJ/cm 2 was 4.57, and the anisotropy value at 400 mJ/cm 2 was 3.03. The irradiation amount of the ultraviolet rays which is the largest in the anisotropy is 300 mJ/cm 2 , which is the most suitable irradiation condition under the light alignment treatment.

(比較例7) (Comparative Example 7)

除了使用上述液晶配向劑(6)以外，與實施例5以相同方式實施後而得到液晶配向膜。測定相對於所得的液晶配向膜之配向方向之異向性的大小。上述紫外線之照射量係在300mJ/cm2之異向性值為0.54、在400mJ/cm2之異向性值為0.65、在500mJ/cm2之異向性值為0.60。異向性成為最大之上述紫外線之照射量係400mJ/cm2，作為在光配向處理下之最適當照射條件。 A liquid crystal alignment film was obtained in the same manner as in Example 5 except that the above liquid crystal alignment agent (6) was used. The magnitude of the anisotropy in the alignment direction with respect to the obtained liquid crystal alignment film was measured. The ultraviolet irradiation amount was such that the anisotropy value at 300 mJ/cm 2 was 0.54, the anisotropy value at 400 mJ/cm 2 was 0.65, and the anisotropy value at 500 mJ/cm 2 was 0.60. The irradiation amount of the ultraviolet rays which is the largest in the anisotropy is 400 mJ/cm 2 , which is the most suitable irradiation condition under the light alignment treatment.

(比較例8) (Comparative Example 8)

除了使用上述液晶配向劑(7)以外，與實施例5以相同方式實施後而得到液晶配向膜。測定相對於所得的液晶配向膜之配向方向之異向性的大小。上述紫外線之照射量係在400mJ/cm2之異向性值為1.61、在600mJ/cm2之異 向性值為1.71、在800mJ/cm2之異向性值為1.59。異向性成為最大上述紫外線之照射量係600mJ/cm2，作為在光配向處理下之最適當照射條件。 A liquid crystal alignment film was obtained in the same manner as in Example 5 except that the above liquid crystal alignment agent (7) was used. The magnitude of the anisotropy in the alignment direction with respect to the obtained liquid crystal alignment film was measured. The ultraviolet irradiation system of the 400mJ / cm 2 of different anisotropy value of 1.61, at 600mJ / cm 2 of different anisotropy value of 1.71, at 800mJ / cm 2 of different anisotropy value of 1.59. The anisotropy is the maximum irradiation amount of the ultraviolet rays of 600 mJ/cm 2 as the most suitable irradiation condition under the photoalignment treatment.

於實施例5~7及比較例5~8中，將測定相對於所得的液晶配向膜之配向方向之異向性的大小結果匯整於表1來表示。 In Examples 5 to 7 and Comparative Examples 5 to 8, the results of measuring the anisotropy of the alignment direction with respect to the obtained liquid crystal alignment film were summarized in Table 1.

(實施例8) (Example 8)

用1.0μm的過濾器將上述液晶配向劑(1)過濾後，於已準備的附有上述電極之基板與背面成膜有ITO膜之具有高度4μm的柱狀間隔物之玻璃基板上，予以旋轉塗佈來進行塗佈。於80℃的加熱板上使其乾燥5分鐘後，用230℃的熱風循環式烘箱進行20分鐘燒成來形成膜厚100nm的塗膜。介隔著偏光板對於此塗膜面照射以消光比26：1的直線偏光之波長254nm的紫外線0.3J/cm2。之 後，於230℃的加熱板上加熱14分鐘後可得到附有液晶配向膜之基板。以上述2片基板為一組，於基板上印刷密封劑，將另一片基板以液晶配向膜面互為對向且配向方向成為0°之方式來貼合後，使密封劑硬化製作空晶胞。對此空晶胞藉由減壓注入法注入液晶MLC-7026-100(Merck公司製)，並將注入口密封後可得到FFS驅動液晶晶胞。之後，將所得的液晶晶胞以110℃加熱1小時後，放置一晚並實施長期交流驅動之殘影評估。於長期交流驅動後此液晶晶胞的角度△值為0.04度。又，進行晶胞中的輝點觀察之結果，輝點的數目未滿10個故為良好。 The liquid crystal alignment agent (1) was filtered through a 1.0 μm filter, and then rotated on a prepared glass substrate having a substrate having the above electrode and a columnar spacer having an ITO film and having a height of 4 μm. Coating to coat. After drying on a hot plate at 80 ° C for 5 minutes, the film was fired in a hot air circulating oven at 230 ° C for 20 minutes to form a coating film having a thickness of 100 nm. The coating film surface was irradiated with ultraviolet rays having a wavelength of 254 nm at an extinction ratio of 26:1 with a polarizing plate of 0.3 J/cm 2 at a wavelength of 254 nm. Thereafter, after heating on a hot plate at 230 ° C for 14 minutes, a substrate with a liquid crystal alignment film was obtained. The sealant is printed on the substrate by using the two substrates as one set, and the other substrate is bonded so that the liquid crystal alignment film faces each other and the alignment direction becomes 0°, and then the sealant is hardened to form an empty cell. . The empty cell was injected into the liquid crystal MLC-7026-100 (manufactured by Merck) by a pressure reduction 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 then left overnight and subjected to long-term AC driving afterimage evaluation. The angle Δ of the liquid crystal cell after long-term AC driving is 0.04 degrees. Further, as a result of observing the bright spot in the unit cell, the number of bright spots was less than ten, which was good.

(實施例9) (Example 9)

除了使用上述液晶配向劑(2)以外，用與實施例8相同之方法來形成膜厚100nm的塗膜。介隔著偏光板對於此塗膜面照射以消光比26：1的直線偏光之波長254nm的紫外線0.1J/cm2後，於230℃的加熱板上加熱14分鐘可得到附有液晶配向膜之基板。除了使用附有此液晶配向膜之基板以外，用與實施例8相同之方法來製作FFS驅動液晶晶胞，並對於所得的晶胞實施長期交流驅動之殘影評估。於長期交流驅動後此液晶晶胞的角度△值為0.10度。又，進行晶胞中的輝點觀察之結果，輝點的數目未滿10個故為良好。 A coating film having a film thickness of 100 nm was formed in the same manner as in Example 8 except that the above liquid crystal alignment agent (2) was used. The coated film surface was irradiated with 0.16/cm 2 of ultraviolet light having a wavelength of 254 nm at a linear extinction ratio of 26:1 with a polarizing plate, and then heated on a hot plate at 230° C. for 14 minutes to obtain a liquid crystal alignment film. Substrate. An FFS-driven liquid crystal cell was fabricated in the same manner as in Example 8 except that the substrate to which the liquid crystal alignment film was attached was used, and the obtained unit cell was subjected to long-term AC drive image stick evaluation. The angle Δ of the liquid crystal cell after long-term AC driving is 0.10 degrees. Further, as a result of observing the bright spot in the unit cell, the number of bright spots was less than ten, which was good.

(實施例10) (Embodiment 10)

除了照射偏光紫外線後，使其浸漬於2-丙醇中3分鐘，接著浸漬於純水中1分鐘以外，用與實施例9相同之方法來製作FFS驅動液晶晶胞。對於此FFS驅動液晶晶胞實施長期交流驅動之殘影評估。於長期交流驅動後此液晶晶胞的角度△值為0.08度。又，進行晶胞中的輝點觀察之結果，輝點的數目未滿10個故為良好。 The FFS-driven liquid crystal cell was produced in the same manner as in Example 9 except that the polarized ultraviolet light was irradiated and immersed in 2-propanol for 3 minutes, followed by immersion in pure water for 1 minute. A residual image evaluation of long-term AC driving is performed for this FFS-driven liquid crystal cell. The angle Δ of the liquid crystal cell after long-term AC driving is 0.08 degrees. Further, as a result of observing the bright spot in the unit cell, the number of bright spots was less than ten, which was good.

(實施例11) (Example 11)

除了使用上述液晶配向劑(3)以外，用與實施例8相同之方法來形成膜厚100nm的塗膜。介隔著偏光板對於此塗膜面照射以消光比26：1的直線偏光之波長254nm的紫外線0.1J/cm2後，使其浸漬2-丙醇中3分鐘，接著浸漬於純水中1分鐘。之後，於230℃的加熱板上加熱14分鐘可得到附有液晶配向膜之基板。除了使用附有此液晶配向膜之基板以外，用與實施例8相同之方法來製作FFS驅動液晶晶胞，並對於所得的晶胞實施長期交流驅動之殘影評估。於長期交流驅動後此液晶晶胞的角度△值為0.08度。又，進行晶胞中的輝點觀察之結果，輝點的數目未滿10個故為良好。 A coating film having a film thickness of 100 nm was formed in the same manner as in Example 8 except that the above liquid crystal alignment agent (3) was used. The coated film surface was irradiated with 0.1 J/cm 2 of ultraviolet light having a wavelength of 254 nm at a linear extinction ratio of 26:1 with a polarizing plate, and then immersed in 2-propanol for 3 minutes, followed by immersion in pure water. minute. Thereafter, the substrate was heated on a hot plate at 230 ° C for 14 minutes to obtain a substrate with a liquid crystal alignment film. An FFS-driven liquid crystal cell was fabricated in the same manner as in Example 8 except that the substrate to which the liquid crystal alignment film was attached was used, and the obtained unit cell was subjected to long-term AC drive image stick evaluation. The angle Δ of the liquid crystal cell after long-term AC driving is 0.08 degrees. Further, as a result of observing the bright spot in the unit cell, the number of bright spots was less than ten, which was good.

(比較例9) (Comparative Example 9)

除了使用上述液晶配向劑(4)以外，用與實施例8相同之方法來形成膜厚100nm的塗膜。介隔著偏光板對於此塗膜面照射以消光比26：1的直線偏光之波長254nm 的紫外線0.2J/cm2。之後，於230℃的加熱板上加熱14分鐘可得到附有液晶配向膜之基板。除了使用附有此液晶配向膜之基板以外，用與實施例8相同之方法來製作FFS驅動液晶晶胞，並對於所得的晶胞實施長期交流驅動之殘影評估。於長期交流驅動後此液晶晶胞的角度△值為0.15度。又，進行晶胞中的輝點觀察之結果，輝點的數目為10個以上故為不良。 A coating film having a film thickness of 100 nm was formed in the same manner as in Example 8 except that the above liquid crystal alignment agent (4) was used. The coating film was irradiated with a polarizing plate of 0.2 J/cm 2 at a wavelength of 254 nm of a linearly polarized light having an extinction ratio of 26:1. Thereafter, the substrate was heated on a hot plate at 230 ° C for 14 minutes to obtain a substrate with a liquid crystal alignment film. An FFS-driven liquid crystal cell was fabricated in the same manner as in Example 8 except that the substrate to which the liquid crystal alignment film was attached was used, and the obtained unit cell was subjected to long-term AC drive image stick evaluation. The angle Δ of the liquid crystal cell after long-term AC driving is 0.15 degrees. Further, as a result of observing the bright spot in the unit cell, the number of bright spots is 10 or more, which is a problem.

(比較例10) (Comparative Example 10)

除了使用上述液晶配向劑(5)以外，用與實施例8相同之方法來形成膜厚100nm的塗膜。介隔著偏光板對於此塗膜面照射以消光比26：1的直線偏光之波長254nm的紫外線0.3J/cm2。之後，於230℃的加熱板上加熱14分鐘可得到附有液晶配向膜之基板。除了使用附有此液晶配向膜之基板以外，用與實施例8相同之方法來製作FFS驅動液晶晶胞，並對於所得的晶胞實施長期交流驅動之殘影評估。於長期交流驅動後此液晶晶胞的角度△值為0.20度。又，進行晶胞中的輝點觀察之結果，輝點的數目為10個以上故為不良。 A coating film having a film thickness of 100 nm was formed in the same manner as in Example 8 except that the above liquid crystal alignment agent (5) was used. The coating film surface was irradiated with ultraviolet rays having a wavelength of 254 nm at an extinction ratio of 26:1 with a polarizing plate of 0.3 J/cm 2 at a wavelength of 254 nm. Thereafter, the substrate was heated on a hot plate at 230 ° C for 14 minutes to obtain a substrate with a liquid crystal alignment film. An FFS-driven liquid crystal cell was fabricated in the same manner as in Example 8 except that the substrate to which the liquid crystal alignment film was attached was used, and the obtained unit cell was subjected to long-term AC drive image stick evaluation. The angle Δ of the liquid crystal cell after long-term AC driving is 0.20 degrees. Further, as a result of observing the bright spot in the unit cell, the number of bright spots is 10 or more, which is a problem.

(比較例11) (Comparative Example 11)

除了使用上述液晶配向劑(6)以外，用與實施例8相同之方法來形成膜厚100nm的塗膜。介隔著偏光板對於此塗膜面照射以消光比26：1的直線偏光之波長254nm 的紫外線0.4J/cm2。之後，於230℃的加熱板上加熱14分鐘可得到附有液晶配向膜之基板。除了使用附有此液晶配向膜之基板以外，用與實施例8相同之方法來製作FFS驅動液晶晶胞，並對於所得的晶胞實施長期交流驅動之殘影評估。於長期交流驅動後此液晶晶胞的角度△值為0.20度。又，進行晶胞中的輝點觀察之結果，輝點的數目為10個以上故為不良。 A coating film having a film thickness of 100 nm was formed in the same manner as in Example 8 except that the above liquid crystal alignment agent (6) was used. The coating film was irradiated with a polarizing plate of 0.4 J/cm 2 of ultraviolet light having a wavelength of 254 nm at an extinction ratio of 26:1. Thereafter, the substrate was heated on a hot plate at 230 ° C for 14 minutes to obtain a substrate with a liquid crystal alignment film. An FFS-driven liquid crystal cell was fabricated in the same manner as in Example 8 except that the substrate to which the liquid crystal alignment film was attached was used, and the obtained unit cell was subjected to long-term AC drive image stick evaluation. The angle Δ of the liquid crystal cell after long-term AC driving is 0.20 degrees. Further, as a result of observing the bright spot in the unit cell, the number of bright spots is 10 or more, which is a problem.

(比較例12) (Comparative Example 12)

除了使用上述液晶配向劑(7)以外，用與實施例8相同之方法來形成膜厚100nm的塗膜。介隔著偏光板對於此塗膜面照射以消光比26：1的直線偏光之波長254nm的紫外線0.6J/cm2。之後，於230℃的加熱板上加熱14分鐘可得到附有液晶配向膜之基板。除了使用附有此液晶配向膜之基板以外，用與實施例8相同之方法來製作FFS驅動液晶晶胞，並對於所得的晶胞實施長期交流驅動之殘影評估。於長期交流驅動後此液晶晶胞的角度△值為0.24度。又，進行晶胞中的輝點觀察之結果、輝點的數目為10個以上故為不良。 A coating film having a film thickness of 100 nm was formed in the same manner as in Example 8 except that the above liquid crystal alignment agent (7) was used. The coating film surface was irradiated with ultraviolet rays having a wavelength of 254 nm at an extinction ratio of 26:1 with a polarizing plate of 0.6 J/cm 2 at a wavelength of 254 nm. Thereafter, the substrate was heated on a hot plate at 230 ° C for 14 minutes to obtain a substrate with a liquid crystal alignment film. An FFS-driven liquid crystal cell was fabricated in the same manner as in Example 8 except that the substrate to which the liquid crystal alignment film was attached was used, and the obtained unit cell was subjected to long-term AC drive image stick evaluation. The angle Δ of the liquid crystal cell after long-term AC driving is 0.24 degrees. Further, as a result of observing the bright spot in the unit cell, the number of bright spots is 10 or more, which is a problem.

[產業利用性] [Industry Utilization]

由本發明之液晶配向劑所得的液晶配向膜，係造成對比降低之原因的輝點為少、且可減低於IPS驅動方式或FFS驅動方式之液晶顯示元件中所產生之因交流驅動所致之殘影，可得到殘影特性為優異的IPS驅動方式或FFS驅動方式之液晶顯示元件。 The liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention has a small number of bright spots which causes a decrease in contrast, and can be reduced by the AC drive due to the IPS drive mode or the FFS drive mode. In the case of the image, a liquid crystal display element having an excellent IPS driving method or an FFS driving method can be obtained.

具有本發明之液晶配向膜之液晶顯示元件係可靠性為優異者，故可被廣泛利用在大畫面、要求高精細且高顯示品質之液晶電視或中小型的汽車導航系統或智慧型手機等。 Since the liquid crystal display element having the liquid crystal alignment film of the present invention is excellent in reliability, it can be widely used in a large-screen, high-definition and high-definition liquid crystal television, a small-sized car navigation system, a smart phone, or the like.

尚，此處援用2014年10月28日申請之日本專利申請案2014-219597號說明書、申請專利範圍、及摘要之全部內容，併入作為本發明之說明書之揭示。 The entire disclosure of Japanese Patent Application No. 2014-219597, the entire disclosure of which is hereby incorporated by reference in its entirety in its entirety in its entirety in

Claims (11)

一種液晶配向劑，其特徵係含有選自由聚醯亞胺前驅物及該聚醯亞胺前驅物之醯亞胺化聚合物所成群之至少1種的聚合物(A)，前述聚醯亞胺前驅物係具有下述式(1)所表示之構造單位、與下述式(2)所表示之構造單位， (式(1)、式(2)中，X1及X2係分別獨立為選自由下述式(X1-1)及(X1-2)所表示之構造所成群之至少1種，R1、R2、R3、R4、及R6係分別獨立為氫原子、或碳數1~4的烷基，R5係碳數1~4的烷基，n係1~6的整數) A liquid crystal alignment agent characterized by containing at least one polymer (A) selected from the group consisting of a polyimide precursor and a ruthenium imide precursor of the polyimide precursor, the polyazide The amine precursor system has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). (In the formula (1) and the formula (2), each of X 1 and X 2 is independently at least one selected from the group consisting of the structures represented by the following formulas (X1-1) and (X1-2), and R 1 、 R 2 , R 3 , R 4 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 5 is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6 ) 如請求項1之液晶配向劑，其中，上述式(1)所表示之構造單位之含有比例，相對於上述聚合物(A)之 全構造單位1莫耳而言為10~50莫耳%，且上述式(2)所表示之構造單位之含有比例，相對於上述聚合物(A)之全構造單位1莫耳而言為20~90莫耳%。 The liquid crystal alignment agent of claim 1, wherein the content ratio of the structural unit represented by the above formula (1) is relative to the polymer (A) The total structural unit is 10 to 50 mol% in terms of 1 mol, and the content ratio of the structural unit represented by the above formula (2) is 20 with respect to 1 mol of the total structural unit of the polymer (A). ~90% by mole. 如請求項1或2之液晶配向劑，其中，式(1)所表示之構造單位與下述式(2)所表示之構造單位可存在於相同的聚醯亞胺前驅物中，又，式(1)所表示之構造單位與下述式(2)所表示之構造單位可存在於各別的聚醯亞胺前驅物中。 The liquid crystal alignment agent of claim 1 or 2, wherein the structural unit represented by the formula (1) and the structural unit represented by the following formula (2) may be present in the same polyimine precursor, and further, The structural unit represented by (1) and the structural unit represented by the following formula (2) may be present in each of the polyimine precursors. 如請求項1~3中任一之液晶配向劑，其中，於上述式(1)及(2)中，X1及X2係前述式(X1-2)。 The liquid crystal alignment agent according to any one of claims 1 to 3, wherein, in the above formulas (1) and (2), X 1 and X 2 are the above formula (X1-2). 如請求項1~4中任一之液晶配向劑，其中，於式(1)及式(2)中，R1及R2係碳數1~3的烷基，R3、R4、R5及R6係氫原子，n係1~3的整數。 The liquid crystal alignment agent according to any one of claims 1 to 4, wherein, in the formulae (1) and (2), R 1 and R 2 are an alkyl group having 1 to 3 carbon atoms, and R 3 , R 4 and R 5 and R 6 are hydrogen atoms, and n is an integer of 1 to 3. 如請求項1~5中任一之液晶配向劑，其中，含有聚合物(A)2~10質量%。 The liquid crystal alignment agent according to any one of claims 1 to 5, which contains 2 to 10% by mass of the polymer (A). 如請求項1~6中任一之液晶配向劑，其係光配向用。 The liquid crystal alignment agent according to any one of claims 1 to 6, which is used for photoalignment. 一種液晶配向膜之製造方法，其特徵係對於將如請求項1~7中任一之液晶配向劑塗佈並燒成後所得的膜照射經偏光的紫外線。 A method for producing a liquid crystal alignment film, which is characterized in that a film obtained by applying and baking a liquid crystal alignment agent according to any one of claims 1 to 7 is irradiated with polarized ultraviolet rays. 如請求項7之液晶配向膜，其中，經偏光的紫外線係具有100~800nm的波長。 The liquid crystal alignment film of claim 7, wherein the polarized ultraviolet light has a wavelength of from 100 to 800 nm. 一種液晶顯示元件，其特徵係具有如請求項8或9之液晶配向膜。 A liquid crystal display element characterized by having a liquid crystal alignment film according to claim 8 or 9. 如請求項10之液晶顯示元件，其中，液晶係負型液晶材料。 The liquid crystal display element of claim 10, wherein the liquid crystal is a negative liquid crystal material.
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