TWI707888B - 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 PDFInfo
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- TWI707888B TWI707888B TW105109242A TW105109242A TWI707888B TW I707888 B TWI707888 B TW I707888B TW 105109242 A TW105109242 A TW 105109242A TW 105109242 A TW105109242 A TW 105109242A TW I707888 B TWI707888 B TW I707888B
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- 0 CC(N)=CC=C(C=C*)OCCOc(cc1)ccc1-c(cc1)ccc1N Chemical compound CC(N)=CC=C(C=C*)OCCOc(cc1)ccc1-c(cc1)ccc1N 0.000 description 2
- CVZPNCTYVVZPJH-UHFFFAOYSA-N CCC(C)(CC)c1ccc(C(C)(CC)CC)cc1 Chemical compound CCC(C)(CC)c1ccc(C(C)(CC)CC)cc1 CVZPNCTYVVZPJH-UHFFFAOYSA-N 0.000 description 1
- RBIYSPHVQHWAIW-UHFFFAOYSA-N CCC(C)C(CC1)CCC1C(C)CC Chemical compound CCC(C)C(CC1)CCC1C(C)CC RBIYSPHVQHWAIW-UHFFFAOYSA-N 0.000 description 1
- UUPXGKCWDFILAS-UHFFFAOYSA-N CCC(C)C1CC(C)C(C)CC1 Chemical compound CCC(C)C1CC(C)C(C)CC1 UUPXGKCWDFILAS-UHFFFAOYSA-N 0.000 description 1
- SDFLTYHTFPTIGX-UHFFFAOYSA-N C[n]1c2ccccc2c2c1cccc2 Chemical compound C[n]1c2ccccc2c2c1cccc2 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 description 1
- STXVIIFFMIFKSD-UHFFFAOYSA-N Cc(cc1)ccc1N(CC1)CCN1c1ccc(C)cc1 Chemical compound Cc(cc1)ccc1N(CC1)CCN1c1ccc(C)cc1 STXVIIFFMIFKSD-UHFFFAOYSA-N 0.000 description 1
- NGDMCVXWKKYGRQ-UHFFFAOYSA-N Cc1c(C)c(-c2cccc(C)c2C)ccc1 Chemical compound Cc1c(C)c(-c2cccc(C)c2C)ccc1 NGDMCVXWKKYGRQ-UHFFFAOYSA-N 0.000 description 1
- ONIJFQFZCKJNDH-UHFFFAOYSA-N Cc1c(C)c2ccc(C)c(C)c2cc1 Chemical compound Cc1c(C)c2ccc(C)c(C)c2cc1 ONIJFQFZCKJNDH-UHFFFAOYSA-N 0.000 description 1
- ZCGYYXALUDNWNO-UHFFFAOYSA-N Cc1ccc(CCNC(NCCc2ccc(C)cc2)=O)cc1 Chemical compound Cc1ccc(CCNC(NCCc2ccc(C)cc2)=O)cc1 ZCGYYXALUDNWNO-UHFFFAOYSA-N 0.000 description 1
- RJCAELQILNYFRQ-UHFFFAOYSA-N Nc(cc1)ccc1-c(cc1)ccc1OCCOc(cc1)cnc1N Chemical compound Nc(cc1)ccc1-c(cc1)ccc1OCCOc(cc1)cnc1N RJCAELQILNYFRQ-UHFFFAOYSA-N 0.000 description 1
- NZCVHIXVNRBXIJ-UHFFFAOYSA-N Nc(cc1)ccc1-c(cc1)ccc1OCCOc1cnc(N)nc1 Chemical compound Nc(cc1)ccc1-c(cc1)ccc1OCCOc1cnc(N)nc1 NZCVHIXVNRBXIJ-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N c1ccc2[nH]c3ccccc3c2c1 Chemical compound c1ccc2[nH]c3ccccc3c2c1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
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- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
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- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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- C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
- C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers
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Abstract
提供用以得到即使使用負型液晶時，亦不產生亮點，可得到良好殘像特性之光配向法用之液晶配向膜的液晶配向劑、液晶配向膜及液晶顯示元件。 Provided is a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element for obtaining a liquid crystal alignment film for a photo alignment method that does not produce bright spots even when a negative liquid crystal is used, and can obtain a good residual image characteristic.
一種液晶配向劑，其含有選自由主鏈中具有式(1)表示之構造的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之群的至少1種聚合物。 A liquid crystal alignment agent, which contains at least one selected from the group consisting of a polyimide precursor having a structure represented by formula (1) in the main chain and an imidized polymer of the polyimide precursor polymer.
[化1]-B1-R1-A-R2-B2- (1) [Chemical 1] -B 1 -R 1 -AR 2 -B 2- (1)
(R1、R2為單鍵、-O-、-S-、-NR12-等，R12為氫原子等，A為碳數2~20之伸烷基，B1、B2係分別獨立地為由下述構造中選出之2價有機基，B1與B2不為相同)。 (R 1 and R 2 are single bonds, -O-, -S-, -NR 12 -, etc., R 12 is a hydrogen atom, etc., A is an alkylene group with 2 to 20 carbon atoms, B 1 and B 2 are respectively It is independently a divalent organic group selected from the following structures, and B 1 and B 2 are not the same).
(R4表示碳數1~5之伸烷基，R5表示氫原子等)。 (R 4 represents an alkylene group having 1 to 5 carbon atoms, R 5 represents a hydrogen atom, etc.).
Description
本發明係關於殘像特性良好之液晶顯示元件的製造所用的液晶配向劑、由該液晶配向劑所得到之液晶配向膜、及具有該液晶配向膜之液晶顯示元件。 The present invention relates to a liquid crystal alignment agent used in the manufacture of a liquid crystal display element with good residual image characteristics, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.
光配向法作為無摩擦之配向處理方法，於工業上亦為簡便的製造製程。特別是於IPS(In-Plane-Switching)驅動方式或FFS(Flinge-field-Switching)驅動方式之液晶顯示元件中，藉由使用以上述光配向法所得到之液晶配向膜，相較於以摩擦處理法所得到之液晶配向膜，可期待液晶顯示元件之對比或視野角特性之提高。藉此，可提高液晶顯示元件之性能，而作為值得期望之液晶配向處理方法受到注目。 As a frictionless alignment processing method, the optical alignment method is also a simple manufacturing process in industry. Especially in the IPS (In-Plane-Switching) driving mode or FFS (Flinge-field-Switching) driving mode of the liquid crystal display element, by using the liquid crystal alignment film obtained by the above-mentioned optical alignment method, compared with rubbing The liquid crystal alignment film obtained by the processing method can be expected to improve the contrast or viewing angle characteristics of the liquid crystal display element. Thereby, the performance of the liquid crystal display element can be improved, and it has attracted attention as a promising liquid crystal alignment processing method.
但是，藉由光配向法所得到之液晶配向膜，相較於摩擦所得者，係有對於高分子膜之配向方向的各向異性小的問題。各向異性小時，無法得到充分的液晶配向性，作為液晶顯示元件時，會發生產生殘像等之問題。 However, the liquid crystal alignment film obtained by the photo-alignment method has a problem that the anisotropy of the alignment direction of the polymer film is smaller than that obtained by rubbing. When the anisotropy is small, sufficient liquid crystal orientation cannot be obtained, and when used as a liquid crystal display element, problems such as after-image generation may occur.
另一方面，作為提高藉由光配向法所得到之液晶配向 膜的各向異性之方法，提出有將藉由光照射切斷前述聚醯亞胺之主鏈而生成的低分子量成分，於光照射後予以去除。 On the other hand, to improve the alignment of liquid crystals obtained by the photo-alignment method As a method of film anisotropy, it is proposed to remove the low molecular weight component generated by cutting the main chain of the polyimide by light irradiation after light irradiation.
[專利文獻1]日本特開平9-297313號公報 [Patent Document 1] Japanese Patent Laid-Open No. 9-297313
[專利文獻2]日本特開2011-107266號公報 [Patent Document 2] JP 2011-107266 A
[非專利文獻1]「液晶光配向膜」木戶脇、市村 機能材料Vol.17(1997) No.11 p.13-22 [Non-Patent Document 1] "Liquid Crystal Optical Alignment Film" Kidowaki, Ichimura Functional Materials Vol.17(1997) No.11 p.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，可使於電極上部之透過損失小，提高對比。 In the liquid crystal display element of the IPS driving method or the FFS driving method, the positive type liquid crystal is used in the past, but by using the negative type liquid crystal, the transmission loss at the top of the electrode can be reduced and the contrast can be improved.
將以光配向法所得到之液晶配向膜，使用於利用負型液晶之IPS驅動方式或FFS驅動方式之液晶顯示元件時，期待會具有較以往的液晶顯示元件更高的顯示性能。但是，本發明者探討的結果，得知藉由光照射所致之聚合物的分解，產出各向異性，使液晶配向之所謂使用光分解型液晶配向膜與負液晶來製作液晶顯示元件時，構成藉由偏 光紫外線照射所產生之液晶配向膜的聚合物之分解生成物所由來的顯示不良(亮點)之發生率高。 When the liquid crystal alignment film obtained by the photo-alignment method is used in a liquid crystal display element using an IPS driving method or an FFS driving method using a negative liquid crystal, it is expected to have higher display performance than the conventional liquid crystal display element. However, as a result of investigation by the present inventors, it is known that the decomposition of the polymer caused by light irradiation produces anisotropy, and the so-called photodecomposable liquid crystal alignment film and negative liquid crystal are used to make liquid crystal display elements. , Constituted by partial The occurrence rate of display defects (bright spots) derived from the decomposition products of the polymer of the liquid crystal alignment film generated by the light ultraviolet irradiation is high.
本發明之課題為提供用以得到即使使用負型液晶時，亦不產生亮點，可得到良好殘像特性之光配向法用之液晶配向膜的液晶配向劑、由該液晶配向劑所得到之液晶配向膜、及具備該液晶配向膜之液晶顯示元件。 The subject of the present invention is to provide a liquid crystal alignment agent for obtaining a liquid crystal alignment film for a photo alignment method that does not produce bright spots even when a negative liquid crystal is used, and can obtain a good residual image characteristic, and a liquid crystal obtained from the liquid crystal alignment agent An alignment film, and a liquid crystal display element provided with the liquid crystal alignment film.
本發明者等人，為了解決上述課題進行努力探討的結果，完成了本發明。亦即，本發明係如以下所示。 The inventors of the present invention have completed the present invention as a result of diligent studies to solve the above-mentioned problems. That is, the present invention is as shown below.
1.一種液晶配向劑，其係含有選自由主鏈中具有下述式(1)表示之構造的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之群的至少1種聚合物；[化1]-B1-R1-A-R2-B2- (1) 1. A liquid crystal alignment agent comprising a polyimide precursor having a structure represented by the following formula (1) in the main chain and an imidization polymer of the polyimide precursor At least one polymer of the group; [化1]-B 1 -R 1 -AR 2 -B 2- (1)
(式中，R1及R2係分別獨立地為單鍵、-O-、-S-、-NR12-、酯鍵、醯胺鍵、硫酯鍵、脲鍵、碳酸酯鍵、或胺基甲酸酯鍵，R12為氫原子、或甲基；A為碳數2~20之伸烷基；B1及B2係分別獨立地為由下述構造中選出之2價有機基，B1與B2不為相同構造)；
(式中，R4為碳數1~5之伸烷基；R5為氫原子、甲基、羥基或甲氧基)。 (In the formula, R 4 is an alkylene group with 1 to 5 carbon atoms; R 5 is a hydrogen atom, a methyl group, a hydroxyl group or a methoxy group).
2.如上述1之液晶配向劑，其中前述聚醯亞胺前驅物，為含有下述式(2)之構造單位的聚合物；
(式中，X1為選自由下述式(X1-1)及(X1-2)表示之構造所成之群的至少1種；Y1為前述式(1)表示之2價有機 基；R3為氫原子或碳數1~5之烷基；Z1及Z2係分別獨立地為氫原子、或可具有取代基之，碳數1~10之烷基、碳數2~10之烯基或碳數2~10之炔基)。 (In the formula, X 1 is at least one selected from the group consisting of the structures represented by the following formulas (X1-1) and (X1-2); Y 1 is the divalent organic group represented by the aforementioned formula (1); R 3 is a hydrogen atom or an alkyl group with 1 to 5 carbons; Z 1 and Z 2 are each independently a hydrogen atom or may have a substituent, an alkyl group with 1 to 10 carbons, and an alkyl group with 2 to 10 carbons Alkenyl or alkynyl with 2 to 10 carbons).
3.如上述2之液晶配向劑，其中前述聚醯亞胺前驅物，相對於全部構造單位而言，具有20~100莫耳%之前述式(2)表示之構造單位。 3. The liquid crystal alignment agent according to the above 2, wherein the aforementioned polyimide precursor has 20-100 mol% of the structural unit represented by the aforementioned formula (2) relative to all structural units.
4.如上述2或3之光配向用液晶配向劑，其中X1為下述式(X1-2)；
5.如上述1~4中任一者之液晶配向劑，其中前述式(1)之構造為下述構造。 5. The liquid crystal alignment agent of any one of 1 to 4 above, wherein the structure of the aforementioned formula (1) is the following structure.
(式中，A、R1及R2係與前述相同定義。) (In the formula, A, R 1 and R 2 are the same as defined above.)
6.一種液晶配向膜，其係對將如上述1~5中任一者之液晶配向劑塗佈、燒成而得到之膜，照射經偏光之紫外線而得到。 6. A liquid crystal alignment film obtained by irradiating a film obtained by coating and firing the liquid crystal alignment agent of any one of 1 to 5 above and irradiating polarized ultraviolet rays.
7.一種液晶顯示元件，其係具備如上述6之液晶配向膜。 7. A liquid crystal display element comprising the liquid crystal alignment film of 6 above.
8.一種以下述式表示之二胺；
(式中，R1及R2係分別獨立地為單鍵、-O-、-S-、-NR12-、酯鍵、醯胺鍵、硫酯鍵、脲鍵、碳酸酯鍵、或胺基甲酸酯鍵，R12為氫原子或甲基，A為碳數2~20之伸烷基)。 (In the formula, R 1 and R 2 are each independently a single bond, -O-, -S-, -NR 12 -, ester bond, amide bond, thioester bond, urea bond, carbonate bond, or amine Carbamate bond, R 12 is a hydrogen atom or a methyl group, A is an alkylene group with 2 to 20 carbon atoms).
藉由使用本發明之液晶配向劑，可抑制光配向處理時所產生之來自液晶配向膜的分解物所致之亮點，可得到照射感度高，具有優良液晶配向性之液晶配向膜， 可提供無顯示不良，信賴性高之液晶顯示元件。 By using the liquid crystal alignment agent of the present invention, the bright spots caused by the decomposition products of the liquid crystal alignment film generated during the photo-alignment process can be suppressed, and a liquid crystal alignment film with high irradiation sensitivity and excellent liquid crystal alignment can be obtained. Can provide liquid crystal display elements with no display defects and high reliability.
藉由使用本發明之液晶配向劑，可得到上述效果之原因雖不明朗，但推測係因作為構成液晶配向劑之聚合物的原料使用之二胺，藉由具有特定之非對稱構造，因光照射所產生之分解物的溶解性及結晶性會變化之故。 By using the liquid crystal alignment agent of the present invention, the reason for the above-mentioned effects is not clear, but it is presumed that the diamine used as the raw material of the polymer constituting the liquid crystal alignment agent has a specific asymmetric structure. This is because the solubility and crystallinity of the decomposition products produced by irradiation change.
構成本發明之液晶配向劑的聚合物之主鏈中，含有上述式(1)表示之特定構造(以下亦稱為特定構造)。 The main chain of the polymer constituting the liquid crystal alignment agent of the present invention contains the specific structure represented by the above formula (1) (hereinafter also referred to as the specific structure).
[化8]-B1-R1-A-R2-B2- (1) [Chemical 8] -B 1 -R 1 -AR 2 -B 2- (1)
上述式(1)中，R1及R2係分別獨立地為單鍵、-O-、-S-、-NR12-、酯鍵、醯胺鍵、硫酯鍵、脲鍵、碳酸酯鍵、或胺基甲酸酯鍵，R12為氫原子或甲基。A為碳數2~20之伸烷基。B1及B2係分別獨立地為由下述構造中選出之2價有機基，B1與B2不為相同構造。再者，B1及B2藉由不為相同構造，因光照射而產生之分解物的溶解性及結晶性會變化，可抑制來自聚合物之分解成分的亮點。 In the above formula (1), R 1 and R 2 are each independently a single bond, -O-, -S-, -NR 12 -, ester bond, amide bond, thioester bond, urea bond, carbonate bond , Or urethane bond, R 12 is a hydrogen atom or a methyl group. A is an alkylene group with 2-20 carbon atoms. B 1 and B 2 are each independently a divalent organic group selected from the following structures, and B 1 and B 2 are not the same structure. Furthermore, since B 1 and B 2 are not of the same structure, the solubility and crystallinity of the decomposition products generated by light irradiation are changed, and it is possible to suppress bright spots from the decomposition components of the polymer.
上述式中，R4為碳數1~5之伸烷基。R5為氫原子、甲基、羥基或甲氧基)。 In the above formula, R 4 is an alkylene group having 1 to 5 carbon atoms. R 5 is a hydrogen atom, a methyl group, a hydroxyl group or a methoxy group).
再者，上述式(1)中，由液晶配向性之觀點，R1、R2尤以單鍵、-O-、-S-、-NR12-、酯鍵或醯胺鍵較佳；特佳為-O-。又，由液晶配向性之觀點，A較佳為碳鏈2~6之伸烷基、特佳為碳鏈2~4之伸烷基。 Furthermore, in the above formula (1), from the viewpoint of liquid crystal orientation, R 1 and R 2 are particularly preferably single bonds, -O-, -S-, -NR 12 -, ester bonds or amide bonds; Best is -O-. In addition, from the viewpoint of liquid crystal alignment, A is preferably an alkylene group with a carbon chain of 2 to 6, and particularly preferably an alkylene group with a carbon chain of 2 to 4.
上述式中，由液晶配向性之觀點，R4較佳為碳數1~3之伸烷基。由液晶配向性之觀點，R5較佳為氫原子或甲基。 In the above formula, from the viewpoint of liquid crystal orientation, R 4 is preferably an alkylene group having 1 to 3 carbon atoms. From the viewpoint of liquid crystal alignment, R 5 is preferably a hydrogen atom or a methyl group.
上述特定構造，較佳為於聚醯亞胺前驅物之原料的二胺中含有。具有上述特定構造之二胺的具體例子，可列舉下述二胺，但不限定於此等。 The above-mentioned specific structure is preferably contained in the diamine which is the raw material of the polyimide precursor. Specific examples of the diamine having the above-mentioned specific structure include the following diamines, but are not limited to these.
(R5係與前述相同定義)。 (R 5 is the same as defined above).
上述式中，R5及R12，亦包含各自的較佳例子地，為與前述相同定義。 In the above formula, R 5 and R 12 , including their respective preferred examples, have the same definitions as described above.
具有上述特定構造之二胺，由配向性及作為液晶顯示元件時的亮點減少之觀點，尤以具有以下構造之二胺為佳。 The diamine having the above-mentioned specific structure is particularly preferable to the diamine having the following structure from the viewpoint of orientation and reduction of bright spots when used as a liquid crystal display element.
上述式中，R1、R2、A，包含各自之較佳例子地，係如上所述。具有上述特定構造之二胺，尤以以下之二胺為佳。 In the above formula, R 1 , R 2 , and A, including their preferred examples, are as described above. The diamines having the above-mentioned specific structure are particularly preferably the following diamines.
以下詳述上述二胺之主要合成法。再者，以下說明之方法係一例，並不限定於此。 The main synthesis methods of the above-mentioned diamines are detailed below. In addition, the method described below is an example and is not limited to this.
本發明之二胺，如下述反應式所示，係藉由將二硝基化合物還原，將硝基轉換為胺基而得到。再者，下述反應式，係記載實施例中記載之二胺，作為一例。 The diamine of the present invention is obtained by reducing a dinitro compound to convert a nitro group into an amino group as shown in the following reaction formula. In addition, the following reaction formula describes the diamine described in the examples as an example.
將二硝基化合物還原之方法並無特殊限制，可例示使用鈀-碳、氧化鉑、雷氏鎳(Raney nickel)、鉑黑、銠-氧化鋁、硫化鉑碳等作為觸媒，於乙酸乙酯、甲苯、四氫呋喃、二噁烷、醇系等之溶劑中，藉由氫氣、肼、氯化氫等而進行還原之方法。亦可依需要使用高壓釜等於加壓下進行。另一方面，於取代苯環或飽和烴部之氫原子的取代基構造中含有不飽和鍵部位時，使用鈀碳或鉑碳等時，會有該不飽和鍵部位被還原，而成為飽和鍵之虞。因此，較佳為使用還原鐵、錫、氯化錫等之過渡金屬作為觸媒的還原條件。 The method of reducing the dinitro compound is not particularly limited. Examples include the use of palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide on carbon, etc. as a catalyst. A method of reducing with hydrogen, hydrazine, hydrogen chloride, etc. in solvents such as esters, toluene, tetrahydrofuran, dioxane, and alcohols. It can also be carried out under pressure using an autoclave as needed. On the other hand, when the substituent structure of the hydrogen atom in the substituted benzene ring or the saturated hydrocarbon portion contains an unsaturated bond site, when palladium carbon or platinum carbon is used, the unsaturated bond site will be reduced to become a saturated bond The fear. Therefore, it is preferable to use transition metals such as reduced iron, tin, and tin chloride as the reduction conditions of the catalyst.
二硝基化合物之合成中，如下述反應式所示，可藉由使市售之聯苯基衍生物，與鹵素等之脫離基X被取代的硝基苯反應，來得到該二硝基化合物。較佳之脫離基X，可列舉氟原子、氯原子、溴原子、碘原子、甲苯磺酸酯(-OTs)、甲磺酸酯(-OMs)等。 In the synthesis of a dinitro compound, as shown in the following reaction formula, the dinitro compound can be obtained by reacting a commercially available biphenyl derivative with a nitrobenzene substituted with a halogen or other leaving group X . Preferable leaving group X includes fluorine atom, chlorine atom, bromine atom, iodine atom, tosylate (-OTs), mesylate (-OMs) and the like.
上述反應可在鹼存在下進行。所使用之鹼，只要係能夠合成，則無特殊限定，可列舉碳酸鉀、碳酸鈉、碳酸銫、烷氧化鈉、烷氧化鉀、氫氧化鈉、氫氧化鉀、氫化鈉等之無機鹼；吡啶、二甲基胺基吡啶、三甲胺、三乙胺、三丁胺等之有機鹼等。又，依情況，若合併使用如二亞苄基丙酮鈀或二苯基膦基二茂鐵鈀之鈀觸媒或銅觸媒等時，可提高產率。由合成之容易的觀點，較佳為使用碳酸鉀之方法，但該方法以外亦能夠合成，因此合成法並無特別限定。 The above reaction can be carried out in the presence of a base. The base used is not particularly limited as long as it can be synthesized. Examples include inorganic bases such as potassium carbonate, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide, and sodium hydride; pyridine; , Dimethylaminopyridine, trimethylamine, triethylamine, tributylamine and other organic bases. In addition, depending on the situation, if a palladium catalyst such as palladium dibenzylidene acetone or palladium diphenylphosphinoferrocene or a copper catalyst is used in combination, the yield can be improved. From the standpoint of ease of synthesis, a method using potassium carbonate is preferred, but synthesis can also be performed other than this method, so the synthesis method is not particularly limited.
構成本發明之液晶配向劑的聚醯亞胺前驅物，含有下述式(2)之構造單位。 The polyimide precursor constituting the liquid crystal alignment agent of the present invention contains a structural unit of the following formula (2).
X1為選自由下述式(X1-1)及(X1-2)表示之構造所成之群的至少1種。其中，由液晶配向性之觀點，尤以下述式(X1-2)為佳。 X 1 is at least one selected from the group consisting of the structures represented by the following formulas (X1-1) and (X1-2). Among them, from the viewpoint of liquid crystal orientation, the following formula (X1-2) is particularly preferred.
Y1為式(1)表示之2價有機基。 Y 1 is a divalent organic group represented by formula (1).
R3為氫原子或碳數1~5之烷基。具體例子，可列舉甲基、乙基、丙基、i-丙基、n-丁基、i-丁基、s-丁基、t-丁基、n-戊基等。由容易進行加熱所致之醯亞胺化的觀點，R3較佳為氫原子或甲基。 R 3 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. Specific examples include methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl and the like. From the viewpoint of easy imidization by heating, R 3 is preferably a hydrogen atom or a methyl group.
Z1及Z2係分別獨立地為氫原子、或可具有取代基之，碳數1~10之烷基、碳數2~10之烯基或碳數2~10之炔基。烷基的具體例子，可列舉甲基、乙基、丙基、丁基、t-丁基、己基、辛基、癸基、環戊基、環己基、雙環己基等。烯基可列舉將存在於上述烷基之1個以上的CH2-CH2構造取代為CH=CH構造者。具體而言，可列舉乙烯基、烯丙基、1-丙烯基、異丙烯基、2-丁烯基、1,3-丁二烯基、2-戊烯基、2-己烯基、環丙烯基、環戊烯基、環己烯基等。炔基可列舉將存在於前述烷基之1個以上的CH2-CH2構造取代為C≡C構造者。具體而言，可列舉乙炔基、1-丙炔基、2-丙炔基等。 Z 1 and Z 2 are each independently a hydrogen atom, or may have a substituent, an alkyl group with 1 to 10 carbons, an alkenyl group with 2 to 10 carbons, or an alkynyl group with 2 to 10 carbons. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, t-butyl, hexyl, octyl, decyl, cyclopentyl, cyclohexyl, and dicyclohexyl. Examples of the alkenyl group include those in which one or more CH 2 -CH 2 structures existing in the above-mentioned alkyl groups are substituted with CH=CH structures. Specifically, vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclo Propenyl, cyclopentenyl, cyclohexenyl, etc. Examples of the alkynyl group include those in which one or more CH 2 -CH 2 structures existing in the aforementioned alkyl groups are substituted with C≡C structures. Specifically, an ethynyl group, 1-propynyl group, 2-propynyl group, etc. are mentioned.
上述之烷基、烯基、及炔基亦可具有取代基，進一步地，亦可藉由取代基形成環構造。再者，藉由取代基形成環構造，意指取代基彼此或取代基與母骨架之 一部分鍵結而成為環構造。 The aforementioned alkyl group, alkenyl group, and alkynyl group may have a substituent, and further, a ring structure may be formed by the substituent. Furthermore, the formation of a ring structure by substituents means the relationship between the substituents or between the substituents and the parent skeleton A part is bonded to form a ring structure.
取代基之例子，可列舉鹵基、羥基、硫醇基、硝基、芳基、有機氧基、有機硫基、有機矽烷基、醯基、酯基、硫酯基、磷酸酯基、醯胺基、烷基、烯基、炔基等。 Examples of substituents include halogen groups, hydroxyl groups, thiol groups, nitro groups, aryl groups, organooxy groups, organothio groups, organosilyl groups, acyl groups, ester groups, thioester groups, phosphate groups, and amide groups. Group, alkyl, alkenyl, alkynyl, etc.
鹵基可列舉氟原子、氯原子、溴原子或碘原子。 Examples of the halogen group include fluorine atom, chlorine atom, bromine atom or iodine atom.
芳基可列舉苯基。前述之其他取代基亦可進一步取代於該芳基上。 Examples of the aryl group include phenyl. The aforementioned other substituents may be further substituted on the aryl group.
有機氧基可表示以O-R表示之構造。該R可相同亦可相異地，可例示前述之烷基、烯基、炔基、芳基等。前述之取代基亦可進一步取代於此等之R上。具體例子，可列舉甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基等。 The organic oxy group may represent a structure represented by O-R. The R may be the same or different, and examples include the aforementioned alkyl, alkenyl, alkynyl, and aryl groups. The aforementioned substituents may be further substituted on these R. Specific examples include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, and octoxy.
有機硫基可表示以-S-R表示之構造。該R可例示前述之烷基、烯基、炔基、芳基等。前述之取代基亦可進一步取代於此等之R上。具體例子，可列舉甲硫基、乙硫基、丙硫基、丁硫基、戊硫基、己硫基、庚硫基、辛硫基等。 The organothio group can represent a structure represented by -S-R. This R can exemplify the aforementioned alkyl group, alkenyl group, alkynyl group, and aryl group. The aforementioned substituents may be further substituted on these R. Specific examples include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio and the like.
有機矽烷基可表示以-Si-(R)3表示之構造。該R可相同亦可相異地，可例示前述之烷基、烯基、炔基、芳基等。前述之取代基亦可進一步取代於此等之R上。具體例子，可列舉三甲基矽烷基、三乙基矽烷基、三丙基矽烷基、三丁基矽烷基、三戊基矽烷基、三己基矽烷基、戊基二甲基矽烷基、己基二甲基矽烷基等。 The organosilyl group can represent a structure represented by -Si-(R) 3 . The R may be the same or different, and examples include the aforementioned alkyl, alkenyl, alkynyl, and aryl groups. The aforementioned substituents may be further substituted on these R. Specific examples include trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, tripentylsilyl, trihexylsilyl, pentyldimethylsilyl, hexyl two Methylsilyl and so on.
醯基可表示以-C(O)-R表示之構造。該R可例示前述 之烷基、烯基、芳基等。前述之取代基亦可進一步取代於此等之R上。具體例子，可列舉甲醯基、乙醯基、丙醯基、丁醯基、異丁醯基、戊醯基、異戊醯基、苄醯基等。 The acyl group can represent a structure represented by -C(O)-R. The R can exemplify the aforementioned The alkyl, alkenyl, aryl, etc. The aforementioned substituents may be further substituted on these R. Specific examples include formyl, acetyl, propyl, butyryl, isobutyryl, pentanyl, isopentyl, benzyl and the like.
酯基可表示以-C(O)O-R、或-OC(O)-R表示之構造。該R可例示前述之烷基、烯基、炔基、芳基等。前述之取代基亦可進一步取代於此等之R上。 The ester group may represent a structure represented by -C(O)O-R or -OC(O)-R. This R can exemplify the aforementioned alkyl group, alkenyl group, alkynyl group, and aryl group. The aforementioned substituents may be further substituted on these R.
硫酯基可表示以-C(S)O-R、或-OC(S)-R表示之構造。該R可例示前述之烷基、烯基、炔基、芳基等。前述之取代基亦可進一步取代於此等之R上。 The thioester group may represent a structure represented by -C(S)O-R or -OC(S)-R. This R can exemplify the aforementioned alkyl group, alkenyl group, alkynyl group, and aryl group. The aforementioned substituents may be further substituted on these R.
磷酸酯基可表示以-OP(O)-(OR)2表示之構造。該R可相同亦可相異地，可例示前述之烷基、烯基、炔基、芳基等。前述之取代基亦可進一步取代於此等之R上。 The phosphate group can represent a structure represented by -OP(O)-(OR) 2 . The R may be the same or different, and examples include the aforementioned alkyl, alkenyl, alkynyl, and aryl groups. The aforementioned substituents may be further substituted on these R.
醯胺基可表示以-C(O)NH2、或-C(O)NHR、-NHC(O)R、-C(O)N(R)2、-NRC(O)R表示之構造。該R可相同亦可相異地，可例示前述之烷基、烯基、炔基、芳基等。前述之取代基亦可進一步取代於此等之R上。 The amide group may represent a structure represented by -C(O)NH 2 , or -C(O)NHR, -NHC(O)R, -C(O)N(R) 2 , and -NRC(O)R. The R may be the same or different, and examples include the aforementioned alkyl, alkenyl, alkynyl, and aryl groups. The aforementioned substituents may be further substituted on these R.
芳基可列舉與前述之芳基相同者。前述之其他取代基亦可進一步取代於該芳基上。 The aryl group may be the same as the aforementioned aryl group. The aforementioned other substituents may be further substituted on the aryl group.
烷基可列舉與前述之烷基相同者。前述之其他取代基亦可進一步取代於該烷基上。 The alkyl group may be the same as the aforementioned alkyl group. The aforementioned other substituents may be further substituted on the alkyl group.
烯基可列舉與前述之烯基相同者。前述之其他取代基亦可進一步取代於該烯基上。 Examples of the alkenyl group are the same as the aforementioned alkenyl groups. The aforementioned other substituents may be further substituted on the alkenyl group.
炔基可列舉與前述之炔基相同者。前述之其他取代基亦可進一步取代於該炔基上。 The alkynyl group may be the same as the aforementioned alkynyl group. The aforementioned other substituents may be further substituted on the alkynyl group.
一般而言，導入體積大之構造時，有降低胺基之反應性或液晶配向性的可能性，因此作為Z1及Z2，更佳為氫原子、或可具有取代基之碳數1~5之烷基；特佳為氫原子、甲基或乙基。 Generally speaking, when a bulky structure is introduced, there is a possibility of reducing the reactivity of the amine group or the orientation of the liquid crystal. Therefore, Z 1 and Z 2 are preferably hydrogen atoms, or the number of carbon atoms that may have substituents 1~ The alkyl group of 5; particularly preferably a hydrogen atom, a methyl group or an ethyl group.
相對於全部構造單位而言，較佳為具有20~100莫耳%之上述式(2)表示之構造單位，由液晶配向性之觀點，特佳為30~100莫耳%。 Relative to all structural units, the structural unit represented by the above formula (2) having 20-100 mol% is preferred, and from the viewpoint of liquid crystal orientation, it is particularly preferably 30-100 mol%.
構成本發明之液晶配向劑的聚合物，含有上述式(2)之構造單位以外的構造單位時，其構造單位係以下述式(3)表示。 When the polymer constituting the liquid crystal alignment agent of the present invention contains structural units other than the structural unit of the above formula (2), the structural unit is represented by the following formula (3).
R3、Z1及Z2之定義係與上述式(2)相同。 The definitions of R 3 , Z 1 and Z 2 are the same as the above formula (2).
X2為4價有機基，Y2為2價有機基。 X 2 is a tetravalent organic group, and Y 2 is a divalent organic group.
X2為來自四羧酸衍生物之4價有機基，其構造並無特殊限定。聚醯亞胺前驅物中，亦可混合存在有2種以上之X2。若表示X2之具體例，可列舉下述式(X-1)~(X-44)之構造。 X 2 is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. In the polyimide precursor, two or more types of X 2 may be mixed. If a specific example of X 2 is shown, the structure of the following formulas (X-1) to (X-44) can be cited.
上述式(X-1)中之R8~R11，係分別獨立地為氫原子、鹵素原子、碳數1~6之烷基、碳數2~6之烯基、碳數2~6之炔基或苯基。R8~R11為體積大之構造時，有降低液晶配向性之可能性，因此更佳為氫原子、甲基或乙基；特佳為氫原子或甲基。 R 8 ~ R 11 in the above formula (X-1) are each independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbons, an alkenyl group with 2 to 6 carbons, and a group with 2 to 6 carbons. Alkynyl or phenyl. When R 8 to R 11 have a bulky structure, there is a possibility of lowering the alignment of the liquid crystal. Therefore, it is more preferably a hydrogen atom, a methyl group or an ethyl group; particularly preferably a hydrogen atom or a methyl group.
式(3)中，Y2為來自二胺之2價有機基，其構造並無特殊限定。若顯示Y2之構造的具體例子，可列舉下述之(Y-1)~(Y-118)。 In formula (3), Y 2 is a divalent organic group derived from diamine, and its structure is not particularly limited. If a specific example of the structure of Y 2 is shown, the following (Y-1) to (Y-118) can be cited.
(式(Y-109)中，m、n係分別獨立地為1~11之整數，m+n為2~12之整數，式(Y-114)中，h為1~3之整數，式(Y-111)及(Y-117)中，j為0~3之整數)。 (In formula (Y-109), m and n are each independently an integer from 1 to 11, m+n is an integer from 2 to 12, in formula (Y-114), h is an integer from 1 to 3, In (Y-111) and (Y-117), j is an integer from 0 to 3).
使用於本發明之聚醯亞胺前驅物，為由二胺成分與四羧酸衍生物之反應而得到者，可列舉聚醯胺酸或聚醯胺酸酯等。 The polyimide precursor used in the present invention is obtained by the reaction of a diamine component and a tetracarboxylic acid derivative, and examples thereof include polyamide acid or polyamide acid ester.
使用於本發明之聚醯亞胺前驅物的聚醯胺酸，係藉由以下方法製造。 The polyimide used in the polyimide precursor of the present invention is produced by the following method.
具體而言，可藉由將四羧酸二酐與二胺，於有機溶劑之存在下，於-20~150℃、較佳於0~50℃反應30分~24小時、較佳為反應1~12小時來合成。 Specifically, it can be achieved by reacting tetracarboxylic dianhydride and diamine in the presence of an organic solvent at -20~150°C, preferably at 0~50°C, for 30 minutes to 24 hours, preferably reaction 1 ~12 hours to synthesize.
二胺成分與四羧酸成分之反應，通常係於有機溶劑中進行。此時所用之有機溶劑，只要係所生成之聚醯亞胺前驅物會溶解者，則無特殊限定。下述係列舉反應所用之有機溶劑的具體例子，但不限定於此等之例子。例如可列舉N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、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。 The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent. The organic solvent used at this time is not particularly limited as long as the polyimide precursor produced can dissolve. The following series give specific examples of organic solvents used in the reaction, but are not limited to these examples. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethyl ethyl Amide, dimethyl sulfoxide or 1,3-dimethyl-imidazolinone.
又，聚醯亞胺前驅物之溶解性高時，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]表示之有機溶劑。 In addition, when the solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D- 1]~Organic solvent represented by formula [D-3].
式[D-1]中，D1表示碳數1~3之烷基，式[D-2]中，D2表示碳數1~3之烷基，式[D-3]中，D3表示碳數1~4之烷基。 In formula [D-1], D 1 represents an alkyl group with 1 to 3 carbons, in formula [D-2], D 2 represents an alkyl group with 1 to 3 carbons, and in formula [D-3], D 3 Represents an alkyl group with 1 to 4 carbon atoms.
此等溶劑可單獨使用、亦可混合使用。進一步地，即使不溶解聚醯亞胺前驅物之溶劑，亦可於不會析出所生成之聚醯亞胺前驅物的範圍，混合於前述溶劑中使用。又，溶劑中之水分會阻礙聚合反應，進而成為水解所生成之聚醯亞胺前驅物的原因，因此溶劑較佳為使用經脫水乾燥者。 These solvents can be used alone or in combination. Furthermore, even if the solvent does not dissolve the polyimide precursor, it can be mixed and used in the aforementioned solvent in a range where the generated polyimine precursor does not precipitate. In addition, the moisture in the solvent will hinder the polymerization reaction, which will further cause the polyimide precursor produced by the hydrolysis. Therefore, the solvent is preferably dehydrated and dried.
反應系中之聚醯胺酸聚合物的濃度，由不易引起聚合物之析出，且容易得到高分子量體之觀點，較佳為1~30質量%、更佳為5~20質量%。 The concentration of the polyamide acid polymer in the reaction system is preferably 1-30% by mass, more preferably 5-20% by mass from the viewpoint that it is difficult to cause precipitation of the polymer and is easy to obtain a high molecular weight body.
如上述方式所得到之聚醯胺酸，可藉由一邊將反應溶液充分攪拌一邊注入於不良溶劑中，使聚合物析出進行回收。又，可藉由進行數次析出，以不良溶劑洗淨後，常溫或加熱乾燥，來得到精製之聚醯胺酸的粉末。不良溶劑並無特殊限定，可列舉水、甲醇、乙醇、己烷、丁基賽珞蘇、丙酮、甲苯等。 The polyamide acid obtained as described above can be recovered by injecting the reaction solution into a poor solvent while fully stirring the polymer to precipitate the polymer. In addition, by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating, a purified polyamide acid powder can be obtained. Poor solvents are not particularly limited, and examples include water, methanol, ethanol, hexane, butyl serosol, acetone, and toluene.
本發明所用之聚醯亞胺前驅物的聚醯胺酸酯，可藉由以下所示之(1)、(2)或(3)之製法製造。 The polyimide precursor of the polyimide used in the present invention can be produced by the preparation method (1), (2) or (3) shown below.
聚醯胺酸酯可藉由將如前述製造之聚醯胺酸予以酯化來製造。具體而言，可藉由將聚醯胺酸與酯化劑於有機溶劑之存在下，於-20~150℃、較佳為於0~50℃反應30分~24小時、較佳為反應1~4小時來製造。 Polyamide can be produced by esterifying the polyamide produced as described above. Specifically, it can be achieved by reacting polyamide acid and esterifying agent in the presence of an organic solvent at -20~150°C, preferably at 0~50°C for 30 minutes to 24 hours, preferably reaction 1. ~4 hours to manufacture.
酯化劑較佳為可藉由精製而容易去除者，可列舉N,N-二甲基甲醯胺二甲基縮醛、N,N-二甲基甲醯胺二乙基縮醛、N,N-二甲基甲醯胺二丙基縮醛、N,N-二甲基甲醯胺二新戊基丁基縮醛、N,N-二甲基甲醯胺二-t-丁基縮醛、1-甲基-3-p-甲苯基三氮烯、1-乙基-3-p-甲苯基三氮烯、1-丙基-3-p-甲苯基三氮烯、4-(4,6-二甲氧基-1,3,5-三嗪-2-基)-4-甲基嗎啉鎓氯化物等。酯化劑之添加量，相對於聚醯胺酸之重複單位1莫耳而言，較佳為2~6莫耳當量。 The esterification agent is preferably one that can be easily removed by purification, and examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, and N ,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dineopentylbutyl acetal, N,N-dimethylformamide di-t-butyl Acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene, 4- (4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride and the like. The addition amount of the esterification agent is preferably 2-6 molar equivalents relative to 1 mol of the repeating unit of polyamide acid.
有機溶劑可列舉例如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、或前述式[D-1]~式[D-3]表示之溶劑。 Examples of organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethyl Methyl acetamide, dimethyl sulfide or 1,3-dimethyl-imidazolinone. In addition, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the aforementioned formula [D -1]~Solvent represented by formula [D-3].
此等之溶劑可單獨使用、亦可混合使用。進一步地，即使不溶解聚醯亞胺前驅物之溶劑，亦可於所生成之聚醯亞胺前驅物不會析出之範圍，混合於前述溶劑中使用。又，溶劑中之水分會阻礙聚合反應，進而成為水解所生成之聚醯亞胺前驅物的原因，因此溶劑較佳為使用經脫水乾 燥者。 These solvents can be used alone or in combination. Furthermore, even if the solvent does not dissolve the polyimide precursor, it can be mixed and used in the aforementioned solvent in a range where the polyimide precursor does not precipitate. In addition, the moisture in the solvent will hinder the polymerization reaction, and then become the cause of the polyimide precursor produced by the hydrolysis. Therefore, the solvent is preferably dehydrated and dried. Dry person.
上述反應所用之溶劑，由聚合物之溶解性而言，較佳為N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、或γ-丁內酯，此等可使用1種或混合2種以上使用。製造時之濃度，由不易引起聚合物之析出，且容易得到高分子量體之觀點，較佳為1~30質量%、更佳為5~20質量%。 The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone in terms of the solubility of the polymer. Use 1 type or mix 2 or more types. The concentration at the time of manufacture is preferably 1-30% by mass, more preferably 5-20% by mass, from the viewpoint that it is difficult to cause precipitation of the polymer and easy to obtain a high molecular weight body.
聚醯胺酸酯可由四羧酸二酯二氯化物與二胺來製造。 Polyurethane can be produced from tetracarboxylic acid diester dichloride and diamine.
具體而言，可藉由將四羧酸二酯二氯化物與二胺，於鹼與有機溶劑之存在下，於-20~150℃、較佳為於0~50℃，反應30分~24小時、較佳為反應1~4小時來製造。 Specifically, the tetracarboxylic acid diester dichloride and diamine can be reacted for 30 minutes to 24 minutes at -20~150°C, preferably at 0~50°C in the presence of alkali and organic solvent. It is preferably produced by reacting for 1 to 4 hours.
前述鹼可使用吡啶、三乙胺、4-二甲基胺基吡啶等，為了使反應溫和進行，較佳為吡啶。鹼之添加量，由去除容易的量，且容易得到高分子量體之觀點，相對於四羧酸二酯二氯化物而言，較佳為2~4倍莫耳。 As the aforementioned base, pyridine, triethylamine, 4-dimethylaminopyridine, etc. can be used. In order to allow the reaction to proceed gently, pyridine is preferred. The amount of alkali added is preferably 2 to 4 times mol relative to the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
上述反應所用之溶劑，由單體及聚合物之溶解性而言，較佳為N-甲基-2-吡咯啶酮、或γ-丁內酯，此等可使用1種或混合2種以上使用。製造時之聚合物濃度，由不易引起聚合物之析出，且容易得到高分子量體之觀點，較佳為1~30質量%、更佳為5~20質量%。又，為了防止四羧酸二酯二氯化物之水解，聚醯胺酸酯之製造所使用的溶劑，較佳為儘可能經脫水，且較佳為於氮環境中，防止外部氣體混入。 The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone in terms of the solubility of monomers and polymers. These can be used singly or in combination of two or more use. The polymer concentration at the time of manufacture is not easy to cause the precipitation of the polymer, and it is easy to obtain a high molecular weight body, preferably 1-30% by mass, more preferably 5-20% by mass. In addition, in order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used in the manufacture of the polyamide ester is preferably dehydrated as much as possible, and preferably in a nitrogen environment to prevent the mixing of external air.
聚醯胺酸酯，可藉由使四羧酸二酯與二胺聚縮合來製造。 Polyurethane can be produced by polycondensing tetracarboxylic acid diester and diamine.
具體而言，可藉由使四羧酸二酯與二胺，於縮合劑、鹼、及有機溶劑之存在下，於0~150℃、較佳為於0~100℃，反應30分~24小時、較佳為反應3~15小時來製造。 Specifically, the tetracarboxylic acid diester and diamine can be reacted for 30 minutes to 24 minutes at 0~150°C, preferably at 0~100°C in the presence of condensing agent, alkali, and organic solvent. It is preferably produced by reacting for 3 to 15 hours.
前述縮合劑，可使用亞磷酸三苯酯、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-(苯并三唑-1-基)-N,N,N’,N’-四甲基脲鎓 四氟硼酸鹽、O-(苯并三唑-1-基)-N,N,N’,N’-四甲基脲鎓六氟磷酸鹽、(2,3-二氫-2-硫基-3-苯并噁唑基)膦酸二苯酯等。縮合劑之添加量，相對於四羧酸二酯而言，較佳為2~3倍莫耳。 As the aforementioned condensing agent, triphenyl phosphite, dicyclohexyl carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyl diimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'- Tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro -2-sulfanyl-3-benzoxazolyl)phosphonic acid diphenyl ester and the like. The addition amount of the condensing agent is preferably 2 to 3 times mol relative to the tetracarboxylic acid diester.
前述鹼可使用吡啶、三乙胺等之3級胺。鹼之添加量，由去除容易的量，且容易得到高分子量體之觀點，相對於二胺成分而言，較佳為2~4倍莫耳。 As the aforementioned base, tertiary amines such as pyridine and triethylamine can be used. The addition amount of the base is preferably 2 to 4 times mol relative to the diamine component from the viewpoint of easy removal and high molecular weight.
又，上述反應中，藉由添加路易士酸作為添加劑，反應會有效率地進行。作為路易士酸，較佳為氯化鋰、溴化鋰等之鹵化鋰。路易士酸之添加量，相對於二胺成分而言，較佳為0~1.0倍莫耳。 In addition, in the above reaction, by adding Lewis acid as an additive, the reaction proceeds efficiently. As Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferred. The addition amount of Lewis acid is preferably 0 to 1.0 times mol relative to the diamine component.
上述3個聚醯胺酸酯之製造方法中，因可得到高分子量之聚醯胺酸酯，故尤以上述(1)或(2)之製法為 特佳。 Among the above three methods for producing polyamides, since high-molecular-weight polyamides can be obtained, the preparation method of (1) or (2) above is especially Especially good.
如上述方式所得到之聚醯胺酸酯之溶液，可藉由一邊充分攪拌一邊注入不良溶劑中，使聚合物析出。進行數次析出，以不良溶劑洗淨後，常溫或加熱乾燥，可得到經精製之聚醯胺酸酯的粉末。不良溶劑並無特殊限定，可列舉水、甲醇、乙醇、己烷、丁基賽珞蘇、丙酮、甲苯等。 The polyamide acid ester solution obtained as described above can be poured into a poor solvent while stirring sufficiently to precipitate the polymer. After several times of precipitation, washing with a poor solvent, and drying at room temperature or by heating, a refined polyamide ester powder can be obtained. Poor solvents are not particularly limited, and examples include water, methanol, ethanol, hexane, butyl serosol, acetone, and toluene.
本發明所用之聚醯亞胺，可藉由使前述之聚醯胺酸酯或聚醯胺酸予以醯亞胺化來製造。 The polyimide used in the present invention can be produced by imidizing the aforementioned polyamide ester or polyamide acid.
由聚醯胺酸酯製造聚醯亞胺時，於使聚醯胺酸酯溶液、或聚醯胺酸酯樹脂粉末溶解於有機溶劑而得到之聚醯胺酸溶液中添加鹼性觸媒的化學醯亞胺化係簡便的。化學醯亞胺化，因於較低溫進行醯亞胺化反應，且於醯亞胺化之過程中不易引起聚合物之分子量降低，故較佳。 When producing polyimide from polyamide, the chemistry of adding a basic catalyst to the polyamide solution obtained by dissolving the polyamide solution or polyamide resin powder in an organic solvent The imidization is simple. The chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is not likely to decrease during the imidization process.
化學醯亞胺化，可藉由使欲醯亞胺化之聚醯胺酸酯，於有機溶劑中，於鹼性觸媒存在下攪拌來進行。有機溶劑可使用前述聚合反應時所用的溶劑。鹼性觸媒可列舉吡啶、三乙胺、三甲胺、三丁胺、三辛胺等。其中尤以三乙胺，由於具備充分使反應進行的鹼性，故較佳。 Chemical imidization can be performed by stirring the polyamide to be imidized in an organic solvent in the presence of a basic catalyst. As the organic solvent, the solvent used in the aforementioned polymerization reaction can be used. Examples of the alkaline catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, triethylamine is particularly preferred because it has sufficient basicity to allow the reaction to proceed.
進行醯亞胺化反應時的溫度，係-20~140℃、較佳為0~100℃，較佳可以反應時間1~100小時來進行。鹼性觸媒之量，為醯胺酸酯基之0.5~30莫耳倍、較佳為2~20莫耳倍。所得之聚合物之醯亞胺化率，可藉由調節觸媒量、 溫度、反應時間等來控制。於醯亞胺化反應後之溶液中係殘存有所添加之觸媒等，因此較佳為藉由以下所述之手段，將所得之醯亞胺化聚合物回收，以有機溶劑再溶解，來作為本發明之液晶配向劑。 The temperature during the imidization reaction is -20 to 140°C, preferably 0 to 100°C, and preferably can be carried out for a reaction time of 1 to 100 hours. The amount of the alkaline catalyst is 0.5 to 30 mole times of the amide ester group, preferably 2 to 20 mole times. The imidization rate of the obtained polymer can be adjusted by adjusting the amount of catalyst, Temperature, reaction time, etc. are controlled. The added catalyst and the like remain in the solution after the imidization reaction. Therefore, it is preferable to recover the obtained imidization polymer by the method described below and re-dissolve it in an organic solvent. As the liquid crystal alignment agent of the present invention.
由聚醯胺酸製造聚醯亞胺時，於藉由二胺成分與四羧酸二酐之反應而得到之聚醯胺酸的溶液中添加觸媒之化學醯亞胺化係簡便的。化學醯亞胺化，因於較低溫進行醯亞胺化反應，且於醯亞胺化之過程中不易引起聚合物之分子量降低，故較佳。 When producing polyimide from polyamic acid, the chemical imidization system of adding a catalyst to a solution of polyimide obtained by the reaction of a diamine component and tetracarboxylic dianhydride is simple. The chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is not likely to decrease during the imidization process.
化學醯亞胺化，可藉由使欲醯亞胺化之聚醯胺酸，於有機溶劑中，於鹼性觸媒與酸酐之存在下攪拌來進行。有機溶劑可使用前述聚合反應時所用的溶劑。鹼性觸媒可列舉吡啶、三乙胺、三甲胺、三丁胺、三辛胺等。其中尤以吡啶，由於具備使反應進行之適度的鹼性，故較佳。又，酸酐可列舉乙酸酐、偏苯三甲酸酐、苯均四酸酐等。其中尤以乙酸酐，因為反應結束後之精製容易，故較佳。 Chemical imidization can be carried out by stirring the polyamide to be imidized in an organic solvent in the presence of a basic catalyst and acid anhydride. As the organic solvent, the solvent used in the aforementioned polymerization reaction can be used. Examples of the alkaline catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is particularly preferred because it has a moderate basicity to allow the reaction to proceed. Moreover, as an acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. are mentioned. Among them, acetic anhydride is particularly preferred because it is easy to purify after the reaction.
進行醯亞胺化反應時的溫度，係-20~140℃、較佳為0~100℃，較佳可以反應時間1~100小時來進行。鹼性觸媒之量，係醯胺酸基之0.5~30莫耳倍、較佳為2~20莫耳倍，酸酐之量，係醯胺酸基之1~50莫耳倍、較佳為3~30莫耳倍。所得之聚合物之醯亞胺化率，可藉由調節觸媒量、溫度、反應時間等來控制。 The temperature during the imidization reaction is -20 to 140°C, preferably 0 to 100°C, and preferably can be carried out for a reaction time of 1 to 100 hours. The amount of alkaline catalyst is 0.5 to 30 mole times of the amide acid group, preferably 2 to 20 mol times, and the amount of acid anhydride is 1 to 50 mole times of the amide acid group, preferably 3~30 mole times. The imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.
聚醯胺酸酯或聚醯胺酸之醯亞胺化反應後的溶液中，係殘存有所添加之觸媒等，因此較佳為藉由以下 所述之手段，將所得之醯亞胺化聚合物回收，以有機溶劑再溶解，來作為本發明之液晶配向劑。 In the solution after the imidization reaction of polyamide ester or polyamide acid, the added catalyst etc. remain, so it is preferable to use the following In the method described, the obtained imidized polymer is recovered and re-dissolved in an organic solvent to serve as the liquid crystal alignment agent of the present invention.
如上述方式所得之聚醯亞胺的溶液，可藉由一邊充分攪拌一邊注入不良溶劑中，使聚合物析出。進行數次析出，以不良溶劑洗淨後，常溫或加熱乾燥，可得到經精製之聚醯亞胺之粉末。 The polyimide solution obtained as described above can be poured into the poor solvent while stirring sufficiently to precipitate the polymer. After several times of precipitation, washing with a poor solvent, and drying at room temperature or by heating, a refined polyimide powder can be obtained.
不良溶劑並無特殊限定，可列舉甲醇、丙酮、己烷、丁基賽璐蘇、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯、苯等。 The poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellulose, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.
本發明之液晶配向劑，含有選自由主鏈中具有特定構造之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之群的至少1種聚合物。聚合物之分子量，以重量平均分子量(Mw)計，較佳為2,000~500,000、更佳為5,000~300,000、又更佳為10,000~100,000。又，數平均分子量(Mn)，較佳為1,000~250,000、更佳為2,500~150,000、又更佳為5,000~50,000。 The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of a polyimide precursor with a specific structure in the main chain and an imidized polymer of the polyimide precursor. The molecular weight of the polymer, based on the weight average molecular weight (Mw), is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000. In addition, the number average molecular weight (Mn) is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
本發明之液晶配向劑中之聚合物的濃度，可依所欲形成之塗膜厚度的設定來適當變更，但由形成均勻且無缺陷之塗膜的觀點，較佳為1質量%以上，由溶液之保存安定性的觀點，較佳為10質量%以下。聚合物之濃度較佳為2~7質量%。 The concentration of the polymer in the liquid crystal alignment agent of the present invention can be appropriately changed according to the setting of the coating film thickness to be formed, but from the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by mass or more. From the viewpoint of the storage stability of the solution, it is preferably 10% by mass or less. The concentration of the polymer is preferably 2 to 7 mass%.
本發明所用之液晶配向劑中所含有的使聚合 物溶解之有機溶劑(以下亦稱為良溶劑)，只要聚合物會均勻溶解者，則無特殊限定。 The liquid crystal alignment agent used in the present invention polymerizes The organic solvent in which the substance is dissolved (hereinafter also referred to as a good solvent) is not particularly limited as long as the polymer dissolves uniformly.
例如，可列舉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、環戊酮或4-羥基-4-甲基-2-戊酮。其中尤以使用N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、或γ-丁內酯為佳。 For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl Sulfidene, γ-butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. Among them, it is particularly preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone.
進一步地，本發明之聚合物對溶劑之溶解性高時，較佳為使用前述式[D-1]~式[D-3]表示之溶劑。 Furthermore, when the polymer of the present invention has high solubility in a solvent, it is preferable to use the solvent represented by the aforementioned formula [D-1] to formula [D-3].
本發明之液晶配向劑中之良溶劑的含量，較佳為液晶配向劑中所含有的溶劑全體之20~99質量%。其中尤佳為20~90質量%。更佳為30~80質量%。 The content of the good solvent in the liquid crystal alignment agent of the present invention is preferably 20 to 99% by mass of the total solvent contained in the liquid crystal alignment agent. Among them, 20 to 90% by mass is particularly preferred. More preferably, it is 30 to 80% by mass.
本發明之液晶配向劑，只要不損及本發明之效果，則可使用提高塗佈液晶配向劑後之液晶配向膜的塗膜性或表面平滑性之溶劑(亦稱為不良溶劑)。列舉不良溶劑之具體例子，但不限定於此等之例子。 As long as the liquid crystal alignment agent of the present invention does not impair the effects of the present invention, a solvent (also referred to as a poor solvent) that improves the coating properties or surface smoothness of the liquid crystal alignment film after coating the liquid crystal alignment agent can be used. Specific examples of poor solvents are given, but they are not limited to these examples.
例如，可列舉乙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、tert-丁醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊醇、tert-戊醇、3-甲基-2-丁醇、新戊醇、1-己醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己醇、1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、 1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、2-甲基-2,4-戊二醇、2-乙基-1,3-己二醇、二丙基醚、二丁基醚、二己基醚、二噁烷、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚、1,2-丁氧基乙烷、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚、二乙二醇二丁基醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、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、乙二醇單丁基醚、乙二醇單異戊基醚、乙二醇單己基醚、2-(己氧基)乙醇、呋喃甲醇、二乙二醇、丙二醇、丙二醇單丁基醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲基醚乙酸酯、二丙二醇、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇二甲基醚、三丙二醇單甲基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、乙酸2-(2-乙氧基乙氧基)乙酯、二乙二醇乙酸酯、三乙二醇、三乙二醇單甲基醚、三乙二醇單乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、乳酸甲基酯、乳酸乙基酯、乳酸n-丙基酯、乳酸n-丁基酯、乳 酸異戊基酯、前述式[D-1]~式[D-3]表示之溶劑等。 For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1 -Butanol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentanol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol Alcohol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol , 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butane Glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl- 1,3-Hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-Butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentane Ketone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethyl acetate Ethylhexyl ester, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether , Ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexoxy) ethanol, furan methanol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy) Base) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether Base ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl Base ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene two Alcohol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, acetone Ethyl ester, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionate Acid, 3-methoxypropyl propionate, 3-methoxy butyl propionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, milk Isoamyl acid ester, the solvent represented by the aforementioned formula [D-1] to formula [D-3], etc.
其中尤以1-己醇、環己醇、1,2-乙二醇、1,2-丙二醇、丙二醇單丁基醚、乙二醇單丁基醚或二丙二醇二甲基醚為佳。 Among them, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether are particularly preferred.
此等不良溶劑之含量，較佳為液晶配向劑中所含有的溶劑全體之1~80質量%。其中尤以10~80質量%為佳、更佳為20~70質量%。 The content of these poor solvents is preferably 1 to 80% by mass of the total solvent contained in the liquid crystal alignment agent. Among them, 10 to 80% by mass is particularly preferable, and 20 to 70% by mass is more preferable.
本發明之液晶配向劑中，於上述以外，只要不損及本發明之效果之範圍，亦可添加本發明記載之聚合物以外的聚合物、以使液晶配向膜之介電率或導電性等之電特性變化為目的之介電體或導電物質、以提高液晶配向膜與基板之密著性為目的之矽烷偶合劑、以提高作為液晶配向膜時的膜之硬度或緻密度為目的之交聯性化合物、進而以於燒成塗膜時效率良好地進行聚醯亞胺前驅物之加熱所致的醯亞胺化為目的之醯亞胺化促進劑等。 In the liquid crystal alignment agent of the present invention, in addition to the above, as long as the scope of the effects of the present invention is not impaired, a polymer other than the polymer described in the present invention may be added to improve the dielectric constant or conductivity of the liquid crystal alignment film. Dielectric or conductive material for the purpose of changing the electrical characteristics of the film, a silane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, and the purpose of improving the hardness or density of the film when used as the liquid crystal alignment film. Linking compounds, and further, an imidization accelerator for the purpose of efficiently performing the imidization of the polyimide precursor by heating at the time of firing the coating film.
本發明之液晶配向膜，為將上述液晶配向劑塗佈於基板並乾燥、燒成而得到之膜。塗佈本發明之液晶配向劑的基板，只要係透明性高之基板則無特殊限定，可使用玻璃基板、氮化矽基板、壓克力基板、聚碳酸酯基板等之塑膠基板等，由製程簡化的觀點，較佳為使用形成有用於液晶驅動之ITO電極等的基板。又，反射型之液晶顯示元件中，若僅為於單側之基板，則亦可使用矽晶圓等之不透明 物，此時的電極亦可使用鋁等之會反射光的材料。 The liquid crystal alignment film of the present invention is a film obtained by coating the above-mentioned liquid crystal alignment agent on a substrate, drying and firing. The substrate coated with the liquid crystal alignment agent of the present invention is not particularly limited as long as it is a highly transparent substrate. Plastic substrates such as glass substrates, silicon nitride substrates, acrylic substrates, polycarbonate substrates, etc. can be used. From a simplified point of view, it is preferable to use a substrate formed with ITO electrodes for liquid crystal driving. In addition, in reflective liquid crystal display elements, if only a single-sided substrate is used, opaque silicon wafers, etc. can also be used In this case, the electrode can also use a material that reflects light, such as aluminum.
本發明之液晶配向劑之塗佈方法，可列舉旋轉塗佈法、印刷法、噴墨法等。 The coating method of the liquid crystal alignment agent of the present invention includes a spin coating method, a printing method, and an inkjet method.
塗佈液晶配向劑後之乾燥、燒成步驟，可選擇任意之溫度與時間。通常，為了充分去除所含有之有機溶劑，乾燥溫度較佳為50~120℃、乾燥時間較佳為1~10分。又，燒成溫度較佳為150~300℃、燒成時間較佳為5~120分。 Any temperature and time can be selected for the drying and firing steps after coating the liquid crystal alignment agent. Generally, in order to fully remove the organic solvent contained, the drying temperature is preferably 50 to 120° C., and the drying time is preferably 1 to 10 minutes. In addition, the firing temperature is preferably 150 to 300°C, and the firing time is preferably 5 to 120 minutes.
燒成後之膜的厚度，並無特殊限定，但太薄時有損及液晶顯示元件之信賴性的可能性，因此較佳為5~300nm、更佳為10~120nm。 The thickness of the film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be impaired, so it is preferably 5 to 300 nm, more preferably 10 to 120 nm.
液晶配向膜之光配向處理的方法，可列舉對塗膜表面照射於一定方向偏光之放射線，依情況進一步於150~250℃之溫度進行加熱處理，賦予液晶配向能力的方法。放射線可使用具有100~800nm之波長的紫外線及可見光線。其中，較佳為具有100~400nm之波長的紫外線、特佳為具有200~400nm之波長者。又，為了改善液晶配向性，亦可一邊將塗膜基板於50~250℃加熱，同時照射放射線。放射線之照射量，較佳為1~10,000mJ/cm2、特佳為100~5,000mJ/cm2。如上述方式所製作之液晶配向膜，可使液晶分子於一定方向安定地配向。 The photo-alignment treatment method of the liquid crystal alignment film can include a method of irradiating the surface of the coating film with polarized radiation in a certain direction, and further heating treatment at a temperature of 150-250°C depending on the situation, to give the liquid crystal alignment ability. The radiation can use ultraviolet and visible light with a wavelength of 100~800nm. Among them, ultraviolet rays having a wavelength of 100 to 400 nm are preferred, and those having a wavelength of 200 to 400 nm are particularly preferred. In addition, in order to improve the liquid crystal orientation, the coated substrate may be heated at 50 to 250°C while irradiating radiation. The radiation dose is preferably 1 to 10,000 mJ/cm 2 , particularly preferably 100 to 5,000 mJ/cm 2 . The liquid crystal alignment film produced in the above manner can make the liquid crystal molecules align stably in a certain direction.
因為可賦予更高的各向異性，經偏光之紫外線的消光比越高越好。具體而言，於直線偏光之紫外線的消光比，較佳為10：1以上、更佳為20：1以上。 Because it can impart higher anisotropy, the higher the extinction ratio of polarized ultraviolet light, the better. Specifically, the extinction ratio of ultraviolet rays in linear polarization is preferably 10:1 or more, more preferably 20:1 or more.
照射過經偏光之放射線的膜，接著亦可藉由 含有由水及有機溶劑中選出之至少1種的溶劑進行接觸處理。 Film that has been irradiated with polarized radiation, and then can also be Contain at least one solvent selected from water and organic solvents for contact treatment.
接觸處理所使用之溶劑，只要係會溶解藉由光照射所生成之分解物的溶劑，則無特殊限定。具體例子，可列舉水、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、丁基賽珞蘇、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。此等之溶劑亦可合併使用2種以上。由通用性或安全性之觀點，更佳為選自由水、2-丙醇、1-甲氧基-2-丙醇及乳酸乙酯所成之群的至少1種。特佳為水、2-丙醇、或水與2-丙醇之混合溶劑。 The solvent used in the contact treatment is not particularly limited as long as it dissolves the decomposed product produced by light irradiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butane Gycerol, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, etc. . Two or more of these solvents can also be used in combination. From the viewpoint of versatility or safety, it is more preferably at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol, and ethyl lactate. Particularly preferred is water, 2-propanol, or a mixed solvent of water and 2-propanol.
本發明中，照射過經偏光之放射線的膜與含有機溶劑之溶液的接觸處理，可列舉浸漬處理、噴霧(噴灑)處理等，較佳為膜與液體充分接觸之處理。其中尤較佳為10秒~1小時、更佳為1~30分，較佳為於含有有機溶劑之溶液中，將膜予以浸漬處理之方法。接觸處理可為常溫，亦可加溫，但較佳為於10~80℃、更佳為於20~50℃實施。又，可依需要，施以超音波等之提高接觸的手段。 In the present invention, the contact treatment between the film irradiated with polarized radiation and the solution containing the organic solvent may include dipping treatment, spray (spraying) treatment, etc., and treatment in which the film and the liquid are fully contacted is preferred. Among them, it is particularly preferably 10 seconds to 1 hour, more preferably 1 to 30 minutes, and more preferably a method of immersing the film in a solution containing an organic solvent. The contact treatment may be at room temperature or heating, but is preferably carried out at 10 to 80°C, more preferably at 20 to 50°C. In addition, if necessary, ultrasonic waves can be used to improve contact.
接觸處理之後，亦能夠以去除所使用之溶液中的有機溶劑為目的，以水、甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮等之低沸點溶劑進行漂洗(潤洗)或乾燥之任一者、或兩者。 After the contact treatment, it can also be used for the purpose of removing the organic solvent in the used solution, and rinse (rinse) or with low boiling point solvents such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, etc. Either or both of drying.
進一步地，經溶劑接觸處理之膜，亦能夠以溶劑之乾燥及膜中之分子鏈的再配向為目的，於150℃以上加熱。加熱溫度較佳為150~300℃。溫度越高，越促進分子鏈之再配向，但溫度太高時，會有伴隨分子鏈之分解之虞。因此，加熱溫度更佳為180~250℃、特佳為200~230℃。 Furthermore, the film subjected to solvent contact treatment can also be heated above 150°C for the purpose of drying the solvent and realigning the molecular chains in the film. The heating temperature is preferably 150 to 300°C. The higher the temperature, the more the realignment of the molecular chain is promoted, but when the temperature is too high, there is a risk of accompanying the decomposition of the molecular chain. Therefore, the heating temperature is more preferably 180 to 250°C, particularly preferably 200 to 230°C.
加熱之時間太短時，會有無法得到分子鏈再配向之效果的可能性，太長時，會有分子鏈分解的可能性，因此較佳為10秒~30分、更佳為1~10分。 When the heating time is too short, there is a possibility that the molecular chain realignment effect may not be obtained, and when it is too long, there is the possibility of molecular chain decomposition, so it is preferably 10 seconds to 30 minutes, more preferably 1 to 10 Minute.
本發明之液晶顯示元件，係為得到具有由本發明之液晶配向劑所形成之液晶配向膜的基板後，以公知方法製作液晶晶胞，使用該晶胞而作為元件者。 The liquid crystal display element of the present invention is to obtain a substrate having a liquid crystal alignment film formed from the liquid crystal alignment agent of the present invention, then fabricate a liquid crystal cell by a known method, and use the cell as an element.
作為液晶晶胞之製作方法的一例，以下以被動矩陣構造之液晶顯示元件為例來說明。再者，亦可為於構成影像顯示之各畫素部分設有TFT(Thin Film Transistor)等之切換元件的主動矩陣構造之液晶顯示元件。 As an example of a method for fabricating a liquid crystal cell, a liquid crystal display element with a passive matrix structure is taken as an example for description. Furthermore, it can also be a liquid crystal display element of an active matrix structure in which switching elements such as TFT (Thin Film Transistor) are provided in each pixel portion constituting the image display.
首先，準備透明之玻璃製基板，於一方之基板上設置共同電極、另一方之基板上設置節段電極。此等之電極，例如可為ITO電極，以可顯示所期望之影像的方式而被圖型化。接著，於各基板上，以被覆共同電極與節段電極的方式設置絕緣膜。絕緣膜例如可為由藉由溶膠-凝膠法形成之SiO2-TiO2所成之膜。 First, a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate. These electrodes, for example, can be ITO electrodes, and are patterned in a manner that can display a desired image. Next, on each substrate, an insulating film is provided to cover the common electrode and the segment electrode. The insulating film may be, for example, a film made of SiO 2 -TiO 2 formed by a sol-gel method.
接著，於各基板上，形成本發明之液晶配向膜。接著，使另一方之基板，以彼此的配向膜面對向的方式疊合於一方之基板上，將周邊以密封材料接著。為了控制基板間隙，通常較佳為於密封材料中混入間隙物(spacer)。又，較佳為於未設置密封材料之面內部分，亦預先散佈基板間隙控制用之間隙物。又，於密封材料之一部分，通常係設置可自外部填充液晶之開口部。 Next, on each substrate, the liquid crystal alignment film of the present invention is formed. Next, the other substrate is superimposed on the one substrate so that the alignment films face each other, and the periphery is bonded with a sealing material. In order to control the substrate gap, it is generally preferable to mix spacers in the sealing material. In addition, it is preferable to pre-spread spacers for substrate gap control on the inner surface where the sealing material is not provided. In addition, a part of the sealing material is usually provided with an opening that can be filled with liquid crystal from the outside.
接著，通過設置於密封材料之開口部，於以2枚基板與密封材料包圍的空間內注入液晶材料。之後，將該開口部以接著劑密封。注入可使用真空注入法，亦可使用於大氣中利用毛細管現象之方法。接著，進行偏光板之設置。具體而言，係於2枚基板之與液晶層相反側的面，貼附一對偏光板。藉由經過以上步驟，可得到本發明之液晶顯示元件。 Next, through the opening provided in the sealing material, the liquid crystal material is injected into the space surrounded by the two substrates and the sealing material. After that, the opening is sealed with an adhesive. Vacuum injection can be used for injection, or capillary phenomenon can be used in the atmosphere. Next, set up the polarizing plate. Specifically, a pair of polarizing plates are attached to the surfaces of the two substrates opposite to the liquid crystal layer. Through the above steps, the liquid crystal display device of the present invention can be obtained.
本發明中，作為密封劑，例如可使用具有環氧基、丙烯醯基、甲基丙烯醯基、羥基、烯丙基、乙醯基等之反應性基的藉由紫外線照射或加熱而硬化之樹脂。特別以使用具有環氧基與(甲基)丙烯醯基之兩方的反應性基之硬化樹脂系較佳。 In the present invention, as the sealant, for example, those having reactive groups such as epoxy, acryl, methacryl, hydroxy, allyl, acetyl, etc., which are cured by ultraviolet irradiation or heating Resin. Particularly, it is preferable to use a curable resin system having a reactive group of both an epoxy group and a (meth)acryloyl group.
亦可以接著性、耐濕性等之提高為目的，於上述密封劑中摻合無機填充劑。可使用之無機填充劑並無特殊限定，具體而言，可列舉球狀二氧化矽、熔融二氧化矽、結晶二氧化矽、氧化鈦、鈦黑、碳化矽、氮化矽、氮化硼、碳酸鈣、碳酸鎂、硫酸鋇、硫酸鈣、雲母、滑石、 黏土、氧化鋁、氧化鎂、氧化鋯、氫氧化鋁、矽酸鈣、矽酸鋁、矽酸鋰鋁、矽酸鋯、鈦酸鋇、玻璃纖維、碳纖維、二硫化鉬、石棉等。較佳為球狀二氧化矽、熔融二氧化矽、結晶二氧化矽、氧化鈦、鈦黑、氮化矽、氮化硼、碳酸鈣、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氫氧化鋁、矽酸鈣、矽酸鋁等。前述之無機填充劑亦可混合2種以上使用。 For the purpose of improving adhesiveness, moisture resistance, etc., an inorganic filler may be blended into the above-mentioned sealing agent. The inorganic fillers that can be used are not particularly limited. Specifically, they include spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon carbide, silicon nitride, boron nitride, Calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, Clay, alumina, magnesia, zirconia, aluminum hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc. Preferably spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina , Aluminum hydroxide, calcium silicate, aluminum silicate, etc. The aforementioned inorganic fillers can also be used by mixing two or more kinds.
以下列舉實施例，以更詳細說明本發明，但本發明不限定於此等。所使用之化合物的略記係如以下所示。 Examples are listed below to illustrate the present invention in more detail, but the present invention is not limited to these. The abbreviations of the compounds used are as follows.
NMP：N-甲基-2-吡咯啶酮、BCS：丁基賽珞蘇 NMP: N-methyl-2-pyrrolidone, BCS: butyl cerosu
將4-羥基-4‘-硝基聯苯(10.0g、46.5mmol)溶解於DMF(40.0g)，添加碳酸鉀(17.2g、69.7mmol)，將β-溴-4-硝基苯乙醚(17.2g、69.7mmol)之DMF溶液(40.0g)於80℃滴下。 4-hydroxy-4'-nitrobiphenyl (10.0g, 46.5mmol) was dissolved in DMF (40.0g), potassium carbonate (17.2g, 69.7mmol) was added, and β-bromo-4-nitrophenyl ethyl ether ( 17.2 g, 69.7 mmol) of DMF solution (40.0 g) was dropped at 80°C.
直接在80℃攪拌2小時，以高速液體層析(以下略稱為HPLC)確認原料消失。之後，將反應液放冷至室溫，添加水(500.0g)，將析出物過濾，將濾物以水(100.0g)洗淨2次。將所得濾物以MeOH(500.0g)洗淨2次。將析出物過濾，於50℃減壓乾燥，藉以得到4-硝基-4‘-(2-(4-硝基苯氧基)乙氧基)-1,1’-聯苯(DA-1-1)(白色粉末、產量：17.6g、產率：99%)。 It was stirred at 80°C for 2 hours as it was, and the disappearance of the raw materials was confirmed by high-speed liquid chromatography (hereinafter abbreviated as HPLC). After that, the reaction liquid was allowed to cool to room temperature, water (500.0 g) was added, the precipitate was filtered, and the filtrate was washed twice with water (100.0 g). The obtained filtrate was washed twice with MeOH (500.0 g). The precipitate was filtered and dried under reduced pressure at 50°C to obtain 4-nitro-4'-(2-(4-nitrophenoxy)ethoxy)-1,1'-biphenyl (DA-1) -1) (White powder, yield: 17.6 g, yield: 99%).
1H NMR(DMSO-d6)：δ 8.22-8.29(m,4H,C6H4),7.94(d,J=7.2Hz,2H,C6H4),7.79(d,J=8.8Hz,2H,C6H4),7.25-7.15(m,4H,C6H4)4.54-4.45(m,4H,CH2).13C{1H}NMR(DMSO-d6)：δ 164.1,159.6,146.6,146.5, 141.4,130.7,129.1,127.5,126.4,124.5,115.7,115.6,67.8,66.7(each s). 1 H NMR (DMSO-d 6 ): δ 8.22-8.29 (m, 4H, C 6 H 4 ), 7.94 (d, J=7.2 Hz, 2H, C 6 H 4 ), 7.79 (d, J=8.8 Hz ,2H,C 6 H 4 ),7.25-7.15(m,4H,C 6 H 4 )4.54-4.45(m,4H,CH 2 ). 13 C{ 1 H}NMR(DMSO-d 6 ): δ 164.1 , 159.6, 146.6, 146.5, 141.4, 130.7, 129.1, 127.5, 126.4, 124.5, 115.7, 115.6, 67.8, 66.7 (each s).
熔點(DSC)：193℃ Melting point (DSC): 193℃
將DA-1-1(5.0g、13.1mmol)溶解於四氫呋喃(100.0g)，添加5質量%鈀-碳(0.1g)，於氫環境下，於室溫攪拌2小時。以HPLC確認原料消失後，將反應液溶解於四氫呋喃(800.0g)中，將觸媒藉由過濾予以去除後，將濾液濃縮。將析出之固體於庚烷(200.0g)中攪拌、洗淨、過濾。藉由將所得固體乾燥而得到DA-1(白色粉末、產量：4.0g、產率：94%)。 DA-1-1 (5.0 g, 13.1 mmol) was dissolved in tetrahydrofuran (100.0 g), 5 mass% palladium-carbon (0.1 g) was added, and the mixture was stirred at room temperature for 2 hours under a hydrogen environment. After confirming the disappearance of the raw materials by HPLC, the reaction solution was dissolved in tetrahydrofuran (800.0 g), the catalyst was removed by filtration, and the filtrate was concentrated. The precipitated solid was stirred, washed, and filtered in heptane (200.0 g). DA-1 (white powder, yield: 4.0 g, yield: 94%) was obtained by drying the obtained solid.
1H NMR(DMSO-d6)：δ 7.45(d,J=8.8Hz,2H,C6H4),7.29(d,J=8.8Hz,2H,C6H4),6.97(d,J=8.8Hz,2H,C6H4),6.70(d,J=8.8Hz,2H,C6H4),6.62(d,J=8.8Hz,2H,C6H4),6.52(d,J=8.8Hz,2H,C6H4),5.14(s,2H,NH2),4.64(s,2H,NH2),4.24(br,2H,CH2),4.16(br,2H,CH2).13C{1H}NMR(DMSO-d4)：δ 157.2,150.0, 148.2,143.1,133.9,127.7,126.2,116.3,115.9,115.5,115.0,114.4,67.2,66.9(each s). 1 H NMR (DMSO-d 6 ): δ 7.45 (d, J=8.8Hz, 2H, C 6 H 4 ), 7.29 (d, J=8.8 Hz, 2H, C 6 H 4 ), 6.97 (d, J =8.8Hz,2H,C 6 H 4 ),6.70(d,J=8.8Hz,2H,C 6 H 4 ),6.62(d,J=8.8Hz,2H,C 6 H 4 ),6.52(d, J=8.8Hz, 2H, C 6 H 4 ), 5.14 (s, 2H, NH 2 ), 4.64 (s, 2H, NH 2 ), 4.24 (br, 2H, CH 2 ), 4.16 (br, 2H, CH 2 ). 13 C{ 1 H}NMR(DMSO-d 4 ): δ 157.2, 150.0, 148.2, 143.1, 133.9, 127.7, 126.2, 116.3, 115.9, 115.5, 115.0, 114.4, 67.2, 66.9 (each s).
熔點(DSC)：156℃ Melting point (DSC): 156℃
再者，合成例之氫核磁共振(1HNMR、500MHz)係於重氫化二甲基亞碸(DMSO-d6)溶劑中測定，化學位移係顯示以四甲基矽烷為內部標準時的δ值(ppm)。 Furthermore, the hydrogen nuclear magnetic resonance ( 1 HNMR, 500MHz) of the synthesis example was measured in the solvent of deuterated dimethyl sulfide (DMSO-d6), and the chemical shift showed the δ value (ppm) when tetramethylsilane was used as the internal standard. ).
各溶液之黏度，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℃下測定。 The viscosity of each solution was measured using an E-type viscometer (TVE-22H, manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL, a cone rotor TE-1 (1°34', R24), and a temperature of 25°C.
GPC裝置：Shodex公司製(GPC-101)、管柱：Shodex公司製(KD803、KD805之直列)、管柱溫度：50℃、溶離液：N,N-二甲基甲醯胺(作為添加劑，係溴化鋰-水合物(LiBr．H2O)30mmol/L、磷酸．無水結晶(o-磷酸)30mmol/L、四氫呋喃(THF)10ml/L)、流速：1.0ml/分。 GPC device: manufactured by Shodex (GPC-101), column: manufactured by Shodex (in-line of KD803 and KD805), column temperature: 50°C, lysate: N,N-dimethylformamide (as an additive, Lithium bromide-hydrate (LiBr. H 2 O) 30mmol/L, phosphoric acid. Anhydrous crystal (o-phosphoric acid) 30mmol/L, tetrahydrofuran (THF) 10ml/L), flow rate: 1.0ml/min.
檢量線製成用標準樣品：東曹公司製TSK標準聚環氧乙烷(重量平均分子量(Mw)；約900,000、150,000、100,000及30,000)、及Polymer Laboratories公司製 聚乙二醇(峰頂分子量(Mp)；約12,000、4,000及1,000)。 Standard samples for making calibration lines: Tosoh Corporation’s TSK standard polyethylene oxide (weight average molecular weight (Mw); approximately 900,000, 150,000, 100,000, and 30,000), and Polymer Laboratories’ polyethylene glycol (peak top Molecular weight (Mp); approximately 12,000, 4,000, and 1,000).
為了避免波峰重疊，測定係各別測定900,000、 100,000、12,000及1,000之4種類混合的樣品；與150,000、30,000及4,000之3種類混合的樣品共2個樣品。 In order to avoid overlapping peaks, the measurement department measures 900,000, 4 mixed samples of 100,000, 12,000 and 1,000; 2 samples mixed with 3 types of 150,000, 30,000 and 4,000.
製作具備邊緣電場切換(Fringe Field Switching：FFS)模式液晶顯示元件之構成的液晶晶胞。 Fabrication of a liquid crystal cell with a Fringe Field Switching (FFS) mode liquid crystal display element.
準備30mm×50mm之大小、厚度0.7mm之附電極的玻璃基板。於基板上形成作為第1層之構成對向電極且具備整體狀之圖型的ITO電極。於第1層之對向電極之上，形成作為第2層之藉由CVD法所成膜的SiN(氮化矽)膜。第2層之SiN膜的膜厚為500nm，發揮作為層間絕緣膜的功能。於第2層之SiN膜之上，作為第3層，係配置使ITO膜圖型化所形成的梳齒狀之畫素電極，形成第1畫素及第2畫素之2個畫素。各畫素之尺寸，係縱10mm、橫約5mm。此時，第1層之對向電極與第3層之畫素電極，係藉由第2層之SiN膜的作用而電性絕緣。 Prepare a glass substrate with electrodes with a size of 30mm×50mm and a thickness of 0.7mm. An ITO electrode with an integral pattern as the first layer constituting the counter electrode is formed on the substrate. On the counter electrode of the first layer, a SiN (silicon nitride) film formed by the CVD method is formed as the second layer. The SiN film of the second layer has a thickness of 500 nm and functions as an interlayer insulating film. On the second layer of SiN film, as the third layer, comb-shaped pixel electrodes formed by patterning the ITO film are arranged to form two pixels, the first pixel and the second pixel. The size of each pixel is 10mm in length and 5mm in width. 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，係具有將中央部分彎曲之ㄑ字形狀的電極要素複數排列所構成的梳齒狀形狀。各電極要素之短邊方向的寬度為3μm，電極要素間之間隔為6μm。形成各畫素之畫素電極，係將中央部分彎曲之ㄑ字形狀的電極要素複數排列所構成，因此各畫素之形狀並非長方形，而係具備類似與電極要素同樣地於中央部分彎曲之粗字的ㄑ字之形狀。此外，各畫素係以其中央之彎曲部 分為界而被上下分割，具有彎曲部分之上側的第1區域與下側的第2區域。 The pixel electrode of the third layer has a comb-tooth shape formed by arranging a plurality of electrode elements in the shape of a U-shaped curved center. The width of each electrode element in the short-side direction is 3 μm, and the interval between the electrode elements is 6 μm. The pixel electrode forming each pixel is constructed by arranging a plurality of electrode elements in the shape of "U" with a curved central part. Therefore, the shape of each pixel is not rectangular, but has a thickness similar to the electrode element that is curved in the central part. The zigzag shape of the word. In addition, each pixel is based on its central curved part It is divided into boundaries and divided up and down, and has a first area on the upper side of the curved portion and a second area on the lower side.
比較各畫素之第1區域與第2區域時，構成該等之畫素電極的電極要素之形成方向係成為不同者。亦即，以後述之液晶配向膜之摩擦方向為基準時，於畫素之第1區域，畫素電極之電極要素係以呈+10°之角度(順時針)的方式形成，於畫素之第2區域，畫素電極之電極要素係以呈-10°之角度(順時針)的方式形成。亦即，於各畫素之第1區域與第2區域，畫素電極與對向電極之間藉由電壓施加所誘發之液晶於基板面內的旋轉動作(面內切換)之方向，係以互相成為反方向的方式構成。 When comparing the first area and the second area of each pixel, the formation directions of the electrode elements constituting the pixel electrodes are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, in the first area of the pixel, the electrode elements of the pixel electrode are formed at an angle of +10° (clockwise). In the second area, the electrode elements of the pixel electrodes are formed at an angle of -10° (clockwise). That is, in the first area and the second area of each pixel, the direction of the rotation (in-plane switching) of the liquid crystal in the substrate surface induced by the voltage application between the pixel electrode and the counter electrode is It is constructed in the opposite direction to each other.
接著，將液晶配向劑以1.0μm之濾器過濾後，以旋轉塗佈塗佈於所準備之上述附電極之基板、與背面成膜有ITO膜之具有高4μm的柱狀間隙物之玻璃基板。塗佈後，於80℃之加熱板上乾燥5分鐘後，於230℃之熱風循環式烘箱進行20分鐘燒成，形成膜厚100nm之塗膜。對該塗膜面，隔著偏光板照射消光比10：1以上之直線偏光的波長254nm之紫外線。將該基板浸漬於由水及有機溶劑中選出之至少1種溶劑中3分鐘，接著於純水中浸漬1分鐘，之後，於150~300℃之加熱板上加熱5分鐘，得到附有液晶配向膜之基板。 Next, the liquid crystal alignment agent was filtered with a 1.0 μm filter, and then spin-coated on the prepared substrate with electrodes, and a glass substrate with an ITO film formed on the back surface with a columnar spacer having a height of 4 μm. After coating, it was dried on a hot plate at 80°C for 5 minutes, and then fired in a hot-air circulating oven at 230°C for 20 minutes to form a coating film with a thickness of 100nm. The coating film surface was irradiated with ultraviolet rays with a wavelength of 254 nm of linearly polarized light having an extinction ratio of 10:1 or more through a polarizing plate. The substrate is immersed in at least one solvent selected from water and organic solvents for 3 minutes, then immersed in pure water for 1 minute, and then heated on a hot plate at 150-300°C for 5 minutes to obtain an alignment with liquid crystal The substrate of the film.
以2枚基板為一組，於一方之基板上印刷密封劑，將另一方之基板，以液晶配向膜面互為對向，且配向方向成為0°的方式貼合後，使密封劑硬化來製作空晶 胞。對該空晶胞，藉由減壓注入法注入液晶MLC-7026-100(Merck公司製)，將注入口密封，得到FFS驅動液晶晶胞。之後，將所得之液晶晶胞於110℃加熱1小時，放置一晚後使用於各評估。 Use two substrates as a set, print a sealant on one of the substrates, and affix the other substrate so that the liquid crystal alignment film faces each other and the alignment direction becomes 0°, and then the sealant is hardened. Make empty crystal Cell. Into this empty cell, liquid crystal MLC-7026-100 (manufactured by Merck) was injected by a reduced pressure injection method, and the injection port was sealed to obtain an FFS driven liquid crystal cell. After that, the obtained liquid crystal cell was heated at 110° C. for 1 hour and left overnight and used for each evaluation.
準備與上述液晶晶胞相同構造之液晶晶胞，於60℃之恆溫環境下，以頻率60Hz施加±5V之交流電壓120小時。之後，使液晶晶胞之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。 Prepare a liquid crystal cell with the same structure as the above liquid crystal cell, and apply an AC voltage of ±5V at a frequency of 60 Hz for 120 hours under a constant temperature environment of 60°C. After that, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and they were left at room temperature for one day.
放置後，將液晶晶胞設置於以偏光軸直交的方式配置之2枚偏光板之間，於電壓無施加之狀態預先點亮背光，調整液晶晶胞之配置角度，使透過光之輝度成為最小。然後，算出使液晶晶胞由第1畫素之第2區域為最暗的角度起旋轉至第1區域為最暗的角度時的旋轉角度，作為角度△。於第2畫素，亦與第1畫素時相同地，比較第2區域與第1區域，算出同樣的角度△。 After placement, the liquid crystal cell is placed between the two polarizing plates arranged in a way that the polarization axis is perpendicular to each other. The backlight is pre-lighted when no voltage is applied, and the arrangement angle of the liquid crystal cell is adjusted to minimize the brightness of the transmitted light. . Then, the rotation angle when the liquid crystal cell is rotated from the angle where the second area of the first pixel is the darkest to the angle where the first area is the darkest is calculated as the angle Δ. For the second pixel, as in the case of the first pixel, the second area and the first area are compared, and the same angle Δ is calculated.
進行上述液晶晶胞之亮點的評估。液晶晶胞之亮點的評估，係藉由以偏光顯微鏡(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寇設置，以倍率設為5倍之偏光顯微鏡觀察液晶晶胞，計數所確認之亮點數目，亮點數未達10個為「良 好」、其以上則為「不良」。 The evaluation of the bright spot of the above-mentioned liquid crystal cell was performed. The evaluation of the bright spot of the liquid crystal cell was performed by observing the liquid crystal cell with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation). Specifically, the liquid crystal cell is set with a crossed Nico, and the liquid crystal cell is observed with a polarizing microscope with a magnification of 5 times, and the number of bright spots confirmed is counted. The number of bright spots is less than 10 as "good Good", above it is "bad".
於附有攪拌裝置及附有氮導入管之50mL四口燒瓶中，量取DA-1 1.44g(4.50mmol)、及DA-2 0.49g(4.53mmol)，添加NMP 25.38g，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1.92g(8.56mmol)，進一步地以固體成分濃度成為12質量%的方式添加NMP 2.82g，於室溫攪拌24小時，得到聚醯胺酸溶液(A)。該聚醯胺酸溶液於溫度25℃之黏度為1680mPa．s。又，該聚醯胺酸之分子量為Mn=14700、Mw=35000。 In a 50mL four-necked flask with a stirring device and a nitrogen introduction tube, weigh out 1.44g (4.50mmol) of DA-1 and 0.49g (4.53mmol) of DA-2, add 25.38g of NMP, and add nitrogen at the same time Stir while dissolving. While stirring the diamine solution, 1.92 g (8.56 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and the solid content concentration was further reduced to 12% by mass Add 2.82g of NMP in the same manner as above, and stir at room temperature for 24 hours to obtain a polyamide acid solution (A). The viscosity of the polyamide acid solution at a temperature of 25°C is 1680mPa. s. In addition, the molecular weight of the polyamide acid is Mn=14,700 and Mw=35,000.
於附有攪拌裝置及附有氮導入管之50mL四口燒瓶中，量取DA-1 2.24g(7.00mmol)，添加NMP 24.64g，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1.49g(6.65mmol)，進一步地以固體成分濃度成為12質量%的方式添加NMP 2.73g，於室溫攪拌24小時，得到聚醯胺酸溶液(B)。該聚醯胺酸溶液於溫度25℃之黏度為2650mPa．s。又，該聚醯胺酸之分子量為Mn=21300、Mw=52300。 In a 50 mL four-necked flask with a stirring device and a nitrogen introduction tube, weigh 2.24 g (7.00 mmol) of DA-1, add 24.64 g of NMP, and stir while feeding nitrogen to dissolve it. While stirring the diamine solution, 1.49 g (6.65 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and the solid content concentration was further adjusted to 12% by mass 2.73g of NMP was added in the manner of, and stirred at room temperature for 24 hours to obtain a polyamide acid solution (B). The viscosity of the polyamide acid solution at a temperature of 25°C is 2650mPa. s. In addition, the molecular weight of the polyamide acid is Mn=21,300 and Mw=52,300.
於附有攪拌裝置及附有氮導入管之50mL四口燒瓶中，量取DA-1 1.51g(4.71mmol)、及DA-3 1.14g(4.71mmol)，添加NMP 16.99g，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2.07g(9.23mmol)，進一步地以固體成分濃度成為20質量%的方式添加NMP 1.89g，於40℃攪拌24小時，得到聚醯胺酸溶液(C)。該聚醯胺酸溶液於溫度25℃之黏度為5000mPa．s。又，該聚醯胺酸之分子量為Mn=13900、Mw=34100。 In a 50mL four-necked flask with a stirring device and a nitrogen introduction tube, weigh out 1.51g (4.71mmol) of DA-1 and 1.14g (4.71mmol) of DA-3, add 16.99g of NMP, and add nitrogen at the same time Stir while dissolving. While stirring the diamine solution, 2.07 g (9.23 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and the solid content concentration was further reduced to 20% by mass 1.89g of NMP was added in the manner of, and stirred at 40°C for 24 hours to obtain a polyamide acid solution (C). The viscosity of the polyamide acid solution at a temperature of 25°C is 5000 mPa. s. In addition, the molecular weight of the polyamide acid is Mn=13900 and Mw=34100.
於附有攪拌裝置及附有氮導入管之50mL四口燒瓶中，量取DA-4 1.59g(6.51mmol)、及DA-2 0.70g(6.47mmol)，添加NMP 33.07g，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2.71g(12.09mmol)，進一步地以固體成分濃度成為12質量%的方式添加NMP 3.67g，於室溫攪拌24小時，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=14500、Mw=30200。 In a 50 mL four-necked flask with a stirring device and a nitrogen introduction tube, weigh out 1.59 g (6.51 mmol) of DA-4 and 0.70 g (6.47 mmol) of DA-2, add 33.07 g of NMP, and add nitrogen while feeding Stir while dissolving. While stirring the diamine solution, 2.71 g (12.09 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and the solid content concentration was further adjusted to 12% by mass 3.67g of NMP was added in the manner of, and stirred at room temperature for 24 hours to obtain a polyamide acid solution (D). The viscosity of the polyamide acid solution at a temperature of 25°C is 360mPa. s. In addition, the molecular weight of the polyamide acid is Mn=14500 and Mw=30200.
於附有攪拌裝置及附有氮導入管之50mL四口燒瓶 中，量取1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐3.59g(16.01mmol)，添加NMP 34.18g，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-2 1.59g(14.70mmol)，進一步地以固體成分濃度成為12質量%的方式添加NMP 3.80g，於室溫攪拌24小時，得到聚醯胺酸溶液(E)。該聚醯胺酸溶液於溫度25℃之黏度為200mPa．s。又，該聚醯胺酸之分子量為Mn=12600、Mw=30500。 In a 50mL four-necked flask with a stirring device and a nitrogen introduction tube Measure 3.59g (16.01mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, add 34.18g of NMP, and stir to dissolve it while feeding nitrogen . While stirring the acid dianhydride solution, 1.59 g (14.70 mmol) of DA-2 was added, and 3.80 g of NMP was further added so that the solid content concentration became 12% by mass, and stirred at room temperature for 24 hours to obtain a polyamide acid solution (E). The viscosity of the polyamide acid solution at a temperature of 25°C is 200mPa. s. In addition, the molecular weight of the polyamide acid is Mn=12600 and Mw=30500.
將12質量%之聚醯胺酸溶液(A)15.00g量取至100ml三角燒瓶中，添加NMP 9.00g及BCS 6.00g，於25℃混合8小時，得到液晶配向劑(1)。液晶配向劑中未見到混濁或析出等之異常，確認為均勻的溶液。 15.00 g of the 12% by mass polyamide acid solution (A) was weighed into a 100 ml Erlenmeyer flask, and 9.00 g of NMP and 6.00 g of BCS were added, and mixed at 25° C. for 8 hours to obtain a liquid crystal alignment agent (1). No abnormalities such as turbidity or precipitation were seen in the liquid crystal alignment agent, and it was confirmed that it was a uniform solution.
除了使用聚醯胺酸溶液(B)以取代聚醯胺酸溶液(A)以外，係與實施例1相同地進行處理，得到液晶配向劑(2)。液晶配向劑中未見到混濁或析出等之異常，確認為均勻的溶液。 Except for using the polyamide acid solution (B) instead of the polyamide acid solution (A), the treatment was performed in the same manner as in Example 1 to obtain a liquid crystal alignment agent (2). No abnormalities such as turbidity or precipitation were seen in the liquid crystal alignment agent, and it was confirmed that it was a uniform solution.
將20質量%之聚醯胺酸溶液(C)9.00g量取至100ml三角燒瓶中，添加NMP 15.00g、BCS 6.00g，於25℃混合 8小時，得到液晶配向劑(3)。液晶配向劑中未見到混濁或析出等之異常，確認為均勻的溶液。 Measure 9.00 g of 20% by mass polyamide acid solution (C) into a 100 ml Erlenmeyer flask, add 15.00 g of NMP and 6.00 g of BCS, and mix at 25°C After 8 hours, the liquid crystal alignment agent (3) was obtained. No abnormalities such as turbidity or precipitation were seen in the liquid crystal alignment agent, and it was confirmed that it was a uniform solution.
除了使用聚醯胺酸溶液(D)以取代聚醯胺酸溶液(A)以外，係與實施例1相同地進行處理，得到液晶配向劑(4)。液晶配向劑中未見到混濁或析出等之異常，確認為均勻的溶液。 Except that the polyamide acid solution (D) was used instead of the polyamide acid solution (A), the treatment was performed in the same manner as in Example 1 to obtain a liquid crystal alignment agent (4). No abnormalities such as turbidity or precipitation were seen in the liquid crystal alignment agent, and it was confirmed that it was a uniform solution.
除了使用聚醯胺酸溶液(E)以取代聚醯胺酸溶液(A)以外，係與實施例1相同地進行處理，得到液晶配向劑(5)。液晶配向劑中未見到混濁或析出等之異常，確認為均勻的溶液。 Except for using the polyamide acid solution (E) instead of the polyamide acid solution (A), the treatment was performed in the same manner as in Example 1 to obtain a liquid crystal alignment agent (5). No abnormalities such as turbidity or precipitation were seen in the liquid crystal alignment agent, and it was confirmed that it was a uniform solution.
將上述液晶配向劑(1)以1.0μm之濾器過濾後，以旋轉塗佈塗佈於上述附電極之基板、與背面成膜有ITO膜之具有高4μm的柱狀間隙物之玻璃基板。接著，於80℃之加熱板上乾燥5分鐘，於230℃之熱風循環式烘箱進行20分鐘燒成，形成膜厚100nm之塗膜。對該塗膜面，隔著偏光板，照射0.2J/cm2之消光比26：1的直線偏光之波長254nm的紫外線。之後，於230℃之加熱板上加熱14分鐘，得到附有液晶配向膜之基板。 After filtering the above liquid crystal alignment agent (1) with a 1.0 μm filter, spin coating was applied to the above substrate with electrodes, and a glass substrate with an ITO film formed on the back side with columnar spacers having a height of 4 μm. Then, it was dried on a hot plate at 80°C for 5 minutes, and fired in a hot-air circulating oven at 230°C for 20 minutes to form a coating film with a thickness of 100 nm. The coating film surface was irradiated with ultraviolet rays having a wavelength of 254 nm with a linearly polarized light with an extinction ratio of 26:1 of 0.2 J/cm 2 through a polarizing plate. After that, it was heated on a hot plate at 230° C. for 14 minutes to obtain a substrate with a liquid crystal alignment film.
以2枚基板為一組，於一方之基板上印刷密封劑，將另一方之基板，以液晶配向膜面互為對向，且配向方向成為0°的方式貼合。之後，使密封劑硬化，製作空晶胞。對該空晶胞，藉由減壓注入法注入液晶MLC-7026-100(Merck公司製)，接著，將注入口密封，得到FFS驅動液晶晶胞。之後，將所得之液晶晶胞於110℃加熱1小時，放置一晚，實施長期交流驅動之殘像評估。長期交流驅動後，該液晶晶胞之角度△之值為0.01°。又，進行液晶晶胞中之亮點觀察的結果，亮點數為未達10個，其係良好。 Using two substrates as a set, a sealant is printed on one substrate, and the other substrate is bonded so that the liquid crystal alignment film faces each other and the alignment direction becomes 0°. After that, the sealant is hardened to produce an empty cell. Into the empty cell, liquid crystal MLC-7026-100 (manufactured by Merck) was injected by a reduced pressure injection method, and then the injection port was sealed to obtain an FFS driven liquid crystal cell. After that, the obtained liquid crystal cell was heated at 110° C. for 1 hour and left overnight to perform long-term AC drive afterimage evaluation. After long-term AC driving, the value of the angle Δ of the liquid crystal cell is 0.01°. In addition, as a result of observing the bright spots in the liquid crystal cell, the number of bright spots was less than 10, and the system was good.
除了使用上述液晶配向劑(2)以外，係以與實施例4相同之方法，形成塗膜。對該塗膜面，隔著偏光板，照射0.5J/cm2之消光比26：1的直線偏光之波長254nm的紫外線。之後，於230℃之加熱板上加熱14分鐘，得到附有液晶配向膜之基板。除了使用該附有液晶配向膜之基板以外，係以與實施例4相同之方法，製作FFS驅動液晶晶胞，對於所得之液晶晶胞實施與實施例4相同之評估。其結果，角度△之值為0.03°。又，亮點數為未達10個，其係良好。 Except for using the above-mentioned liquid crystal alignment agent (2), the coating film was formed in the same manner as in Example 4. The coating film surface was irradiated with ultraviolet rays with a wavelength of 254 nm of linearly polarized light with an extinction ratio of 26:1 of 0.5 J/cm 2 through a polarizing plate. After that, it was heated on a hot plate at 230° C. for 14 minutes to obtain a substrate with a liquid crystal alignment film. Except that the substrate with the liquid crystal alignment film was used, the FFS driving liquid crystal cell was produced in the same manner as in Example 4, and the same evaluation as in Example 4 was performed on the obtained liquid crystal cell. As a result, the value of the angle Δ is 0.03°. In addition, the number of bright spots is less than 10, which is good.
除了使用上述液晶配向劑(3)以外，係以與實施例4 相同之方法，形成塗膜，照射紫外線，加熱而得到附有液晶配向膜之基板。除了使用該附有液晶配向膜之基板以外，係以與實施例4相同之方法，製作FFS驅動液晶晶胞，對於所得之液晶晶胞實施與實施例4相同之評估。其結果，角度△之值為0.02°。又，亮點數為未達10個，其係良好。 In addition to the use of the above-mentioned liquid crystal alignment agent (3), the same as in Example 4 In the same way, a coating film is formed, irradiated with ultraviolet rays, and heated to obtain a substrate with a liquid crystal alignment film. Except that the substrate with the liquid crystal alignment film was used, the FFS driving liquid crystal cell was produced in the same manner as in Example 4, and the same evaluation as in Example 4 was performed on the obtained liquid crystal cell. As a result, the value of the angle Δ is 0.02°. In addition, the number of bright spots is less than 10, which is good.
除了使用上述液晶配向劑(4)以外，係以與實施例4相同之方法，形成塗膜，照射紫外線，加熱而得到附有液晶配向膜之基板。除了使用該附有液晶配向膜之基板以外，係以與實施例4相同之方法，製作FFS驅動液晶晶胞，對於所得之液晶晶胞實施與實施例4相同之評估。其結果，角度△之值為0.10°。又，亮點數為10個以上，其係不良。 Except for using the above-mentioned liquid crystal alignment agent (4), a coating film was formed in the same manner as in Example 4, irradiated with ultraviolet rays, and heated to obtain a substrate with a liquid crystal alignment film. Except that the substrate with the liquid crystal alignment film was used, the FFS driving liquid crystal cell was produced in the same manner as in Example 4, and the same evaluation as in Example 4 was performed on the obtained liquid crystal cell. As a result, the value of the angle Δ is 0.10°. In addition, the number of bright spots is 10 or more, which is not good.
除了使用上述液晶配向劑(5)以外，係以與實施例4相同之方法，形成塗膜，照射0.5J/cm2之紫外線，加熱而得到附有液晶配向膜之基板。除了使用該附有液晶配向膜之基板以外，係以與實施例4相同之方法，製作FFS驅動液晶晶胞，對於所得之液晶晶胞實施與實施例4相同之評估。其結果，角度△之值為0.19°。又，亮點數為10個以上，其係不良。 Except for using the above-mentioned liquid crystal alignment agent (5), a coating film was formed in the same manner as in Example 4, irradiated with 0.5 J/cm 2 ultraviolet rays, and heated to obtain a substrate with a liquid crystal alignment film. Except that the substrate with the liquid crystal alignment film was used, the FFS driving liquid crystal cell was produced in the same manner as in Example 4, and the same evaluation as in Example 4 was performed on the obtained liquid crystal cell. As a result, the value of the angle Δ was 0.19°. In addition, the number of bright spots is 10 or more, which is not good.
本發明之液晶配向劑，能夠形成即使使用負型液晶時，亦不產生亮點，具有良好殘像特性之光配向法用之液晶配向膜，可利用於高顯示品質之FFS驅動方式的液晶顯示元件等。 The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film for optical alignment method with good afterimage characteristics without generating bright spots even when negative liquid crystals are used, and can be used in high display quality liquid crystal display elements of FFS driving mode Wait.
再者，於此係引用2015年3月24日所申請之日本專利申請2015-061095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。 In addition, all the contents of the specification, scope of patent application, and abstract of Japanese Patent Application No. 2015-061095 filed on March 24, 2015 are cited here and incorporated as the disclosure of the specification of the present invention.
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| JP7396177B2 (en) | 2020-04-09 | 2023-12-12 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element |
| TWI834894B (en) * | 2020-07-13 | 2024-03-11 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| KR20230038512A (en) | 2020-07-17 | 2023-03-20 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element |
| JP7311047B2 (en) | 2020-07-17 | 2023-07-19 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
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| JP2022027466A (en) | 2020-07-29 | 2022-02-10 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal element |
| WO2022085674A1 (en) * | 2020-10-23 | 2022-04-28 | 日産化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| KR20240037999A (en) | 2021-07-30 | 2024-03-22 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, compound, and polymer |
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- 2016-03-23 KR KR1020177030346A patent/KR102605000B1/en active IP Right Grant
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| TW200516099A (en) * | 2003-11-05 | 2005-05-16 | Chisso Corp | Diamine |
| TW200521210A (en) * | 2003-11-05 | 2005-07-01 | Chisso Corp | Liquid crystal alignment agent |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016152928A1 (en) | 2016-09-29 |
| JP2020040953A (en) | 2020-03-19 |
| CN107615145B (en) | 2021-05-07 |
| CN107615145A (en) | 2018-01-19 |
| JPWO2016152928A1 (en) | 2018-03-22 |
| TW201708316A (en) | 2017-03-01 |
| JP6669161B2 (en) | 2020-03-18 |
| KR20170131533A (en) | 2017-11-29 |
| CN111777519B (en) | 2023-12-05 |
| KR102605000B1 (en) | 2023-11-22 |
| KR20230097217A (en) | 2023-06-30 |
| JP6852771B2 (en) | 2021-03-31 |
| CN111777519A (en) | 2020-10-16 |
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