TWI299057B - Agent for orienting liquid crystal - Google Patents

Description

1299057 Α7 Β7 五、發明説明（1 ) 技術領域 (請先閲讀背面之注意事項再填寫本頁) 本發明係有關液晶定向劑。更詳言之，係有關電壓保 持特性，低殘像性及印刷性優，具有尤適於垂直定向型液 晶顯示元件用之垂直定向性之液晶定向劑。 先行技術 經濟部智慧財產局員工消費合作社印製 目前，液晶顯示元件已知有，於設有透明導電膜之基 板表面形成聚醯胺酸，聚醯亞胺等所成之液晶定向膜作成 液晶顯示元件用基板，其二片相向配置，於間隙內形成具 正的介電各向異性之向列型液晶層成爲夾層構造之單元， 液晶分子之長軸有如從其一基板朝另一基板連續扭轉9 0 度，具所謂的T N (扭轉向列）型液晶單元之T N型液晶 顯示元件。此外，有成本高於T N型液晶顯示元件，視角 依賴性少之S T N (超級扭轉向列）型液晶顯示元件，及 垂直定向型液晶顯示元件之開發。該S T N型液晶顯示元 件，係於向列型液晶拌合以光學活性物質對掌劑用作液晶 ’利用液晶分子之長軸在基板間成1 8 0度以上之連續扭 轉狀態所產生之複折射效果。相對於此，垂直定向型液晶 顯示元件係例如，液晶分子之介電各向異性爲負之液晶作 垂直定向，施加電壓使液晶分子水平臥倒，具視角，對比 及無平磨等優點，近年來硏發活躍。 爲作垂直定向須有高預傾角，爲此，定向劑中須含大 量之用以展現預傾角之成分。預傾展現成分通常多用脂族 ，脂環族，氟系之官能基。 ^紙張尺度適用中國國家標準（€奶）八4規格（210/297公釐) 771 ' 1299057 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明説明（2) 然而，卻有.因而預傾角展現成分之間起凝集，結晶化 ，使印刷性惡化之類的問題。 因此，印刷性優，且垂直定向性，低殘像性，電壓保 持特性完美之垂直定向劑尙待開發。 發明所欲解決之課題 因而，本發明之目的在提供，印刷性，消泡性優，且 垂直定向性，低殘像性及電壓保持特性良好之液晶定向劑 〇 本發明之其它目的及優點，可由以下之說明得知。 用以解決課題之手段 根據本發明，其上述目的及優點，第一係藉由其特徵 爲：含（A )下式（1 )1299057 Α7 Β7 V. INSTRUCTIONS (1) TECHNICAL FIELD (Please read the precautions on the back and fill out this page.) The present invention relates to a liquid crystal aligning agent. More specifically, it is a liquid crystal aligning agent which is particularly suitable for vertical alignment of a liquid crystal display element for a vertical alignment type, which is excellent in voltage retention characteristics, low afterimage resistance and printability. First, the Ministry of Technology and Economy, the Intellectual Property Bureau, the employee consumption cooperative, printed on the liquid crystal display device. The liquid crystal display element is known to form a liquid crystal alignment film formed on the surface of a substrate provided with a transparent conductive film, such as polylysine or polyimine. The substrate for a device has two sheets facing each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap as a unit of the sandwich structure, and the long axis of the liquid crystal molecules is continuously twisted from one substrate to the other substrate. 90 degrees Celsius, a TN type liquid crystal display element having a so-called TN (twisted nematic) type liquid crystal cell. Further, there is a development of a S T N (super twisted nematic) type liquid crystal display element having a lower cost than a T N type liquid crystal display element, and a vertical alignment type liquid crystal display element. The STN type liquid crystal display element is used for mixing a nematic liquid crystal, and the optically active substance is used as a liquid crystal. The birefringence is generated by a continuous twist state in which the long axis of the liquid crystal molecules is 180 degrees or more between the substrates. effect. On the other hand, the vertical alignment type liquid crystal display element is, for example, a liquid crystal molecule whose dielectric anisotropy is negative, and the liquid crystal is vertically oriented, and the application of a voltage causes the liquid crystal molecules to lie horizontally, having a viewing angle, contrast, and no flat grinding, and the like. Come to be active. A high pretilt angle is required for vertical orientation, and for this purpose, the orientation agent must contain a large amount of ingredients to exhibit the pretilt angle. Pre-tilt exhibiting components usually use aliphatic, alicyclic, and fluorine-based functional groups. ^Paper scale applies to Chinese national standard (€奶) 八4 specification (210/297 mm) 771 ' 1299057 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing Β7 Β7 5, invention description (2) However, there is. The inclination angle exhibits problems such as aggregation and crystallization between components, which deteriorates printability. Therefore, a vertical orientation agent which is excellent in printability, vertical orientation, low afterimage resistance, and excellent voltage retention characteristics needs to be developed. DISCLOSURE OF THE INVENTION Accordingly, an object of the present invention is to provide a liquid crystal aligning agent which is excellent in printability, defoaming property, vertical orientation, low afterimage refraction and voltage retention characteristics, and other objects and advantages of the present invention. It can be known from the following description. Means for Solving the Problems According to the present invention, the above objects and advantages are first characterized by having (A) the following formula (1)

在此，R 1係鹵素原子，碳原子數1至1 〇之烷基或碳原 子數1至1 0之氟化烷基，而a係0至4之整數， 所示之四羧酸二酐（以下亦稱「特定四羧酸二酐」）與 未紙張尺度適用中國國家標準（CNS ) A4規格（2i〇x297公釐) (請先閲讀背面之注意事項再填寫本頁)Here, R 1 is a halogen atom, an alkyl group having 1 to 1 Å carbon atom or a fluorinated alkyl group having 1 to 10 carbon atoms, and a is an integer of 0 to 4, and the tetracarboxylic dianhydride is shown. (hereinafter also referred to as "specific tetracarboxylic dianhydride") and the non-paper scale applicable to the Chinese National Standard (CNS) A4 specification (2i〇x297 mm) (please read the notes on the back and fill out this page)

1299057 A7 B7 五、發明説明（3 ) (B )下式（2 )1299057 A7 B7 V. Description of invention (3) (B) (2)

.(2) »· 經濟部智慧財產局員工消費合作社印製 在此，X係2價有機基，R 2係具碳原子數4至4 0之脂 環骨幹之1價有機基， 所示之二胺（以下亦稱「特定二胺」）反應生成之聚醯胺 酸及該聚醯胺酸脫水閉環生成之醯亞胺化聚合物之至少一 種的液晶定向劑達成。 本發明之液晶定向劑，其較佳者係含1 -甲基- 2 -吡咯烷酮2 0至6 0重量％，表面張力3 2達因/公分以 下之溶劑8 0至4 0重量％的組成之溶劑作爲溶劑。 發明之實施形態 以下詳細說明本發明。 〔聚醯胺酸〕 本發明所用之聚醯胺酸，係以上述式（1 )所示之特 定四羧酸二酐，與上述式（2 )所示之特定二胺開環加聚 而得。 又，本發明所用之醯亞胺化聚合物，係將上述聚醯胺 酸脫水閉環而得。 (請先閱讀背面之注意事項再填寫本頁) ,ιτ 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 1299057 A7 B7 五、發明説明（4 ) 〔四羧酸二酐〕 本發明之液晶定向劑’因使用上述式（1 )所表特定 四羧酸二酐而具低殘像性，電壓保持特性優良之性能。 上述式（1)中，Rl可舉’Br等之鹵素 原子；甲基，乙基，正丙基’異丙基等碳原子數1至1 〇 之烷基；三氟甲基等碳原子數1至1 〇之氟化烷基等。而 ，3係〇至4之整數。 特定四羧酸二酐之具體例可舉1 ’ 2 ’ 3 ’ 4 一環丁 烷四羧酸二酐，1 ，2 —二甲基一1 ，2 ，3 ’4 一環丁 烷四羧酸二酐，1 ，3 —二甲基一 1 ，2 ，3 ’ 4 —環丁 烷四羧酸二酐，1 ，3 —二氯一 1 ，2，3 ’ 4 —環丁烷 四羧酸二酐，1 ，2 ，3 ，4 —四甲基一1 ，2 ，3 ，4 一環丁烷四羧酸二酐等。其中以用1 ，2 ’ 3 ，4 一環丁 院四羧酸二酐，1 ，3 —二甲基—1 ，2 ，3 ，4 —環丁 烷四羧酸二酐爲佳。 上述聚醯胺酸，在無損於本發明之效果的程度’亦可 與其它四羧酸二酐作用。其它之四羧酸二酐可舉例如’丁 烷四羧酸二酐，1 ，2，3，4 —環戊烷四羧酸二酐’ 1 ，2，3，4，5 —環己烷四羧酸二酐，3 ，3，，4， 4 / 一雙環己基四羧酸二酐，順式一3 ，7 —二丁基環辛 —1 ，5 —二烯一1，2，5 ，6 — 四羧酸二酐，2，3 ，5 -三羧基環戊基醋酸二酐，3，5，6 -三羰基一 2 —殘基降冰片烷一 2 : 3，，5 : 6 —二酐，2，3，4 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ297公釐） ' (請先閲讀背面之注意事項再填寫本頁) 4. 訂(2) »· The Intellectual Property Office of the Ministry of Economic Affairs, the employee consumption cooperative, printed here, X is a divalent organic group, and R 2 is a monovalent organic group having an alicyclic backbone with 4 to 40 carbon atoms, as shown. A liquid crystal aligning agent of at least one of a polyamine acid produced by a reaction of a diamine (hereinafter also referred to as "specific diamine") and a ruthenium iodide polymer produced by dehydration ring closure of the polyglycolic acid is obtained. The liquid crystal aligning agent of the present invention is preferably a composition comprising 20 to 60% by weight of 1-methyl-2-pyrrolidone and 80 to 40% by weight of a solvent having a surface tension of 3 2 dynes/cm or less. The solvent acts as a solvent. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Polyuric acid] The polylysine used in the present invention is obtained by subjecting a specific tetracarboxylic dianhydride represented by the above formula (1) to ring-opening polyaddition of a specific diamine represented by the above formula (2). . Further, the ruthenium iodide polymer used in the present invention is obtained by dehydrating and ring-closing the above polyamic acid. (Please read the note on the back and fill out this page), ιτ This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1299057 A7 B7 V. Invention description (4) [Tetracarboxylic dianhydride The liquid crystal aligning agent of the present invention has low afterimage properties and excellent voltage holding characteristics by using the specific tetracarboxylic dianhydride represented by the above formula (1). In the above formula (1), R1 may, for example, be a halogen atom such as 'Br or the like; an alkyl group having 1 to 1 ring of a carbon atom such as a methyl group, an ethyl group or a n-propyl 'isopropyl group; or a carbon atom such as a trifluoromethyl group; 1 to 1 fluorinated alkyl group and the like. However, the 3 series 〇 to an integer of 4. Specific examples of the specific tetracarboxylic dianhydride include 1 ' 2 ' 3 ' 4 -cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3 '4-cyclobutanetetracarboxylic dianhydride 1,1,3-dimethyl- 1,2,3'4-cyclobutanetetracarboxylic dianhydride, 1,3 -dichloro-1,2,3'4-cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4 - tetramethyl-1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, and the like. Among them, 1, 2 ′ 3 , 4 ring butyl tetracarboxylic dianhydride, and 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride are preferred. The above polylysine may also act on other tetracarboxylic dianhydrides to the extent that the effects of the present invention are not impaired. Other tetracarboxylic dianhydrides include, for example, 'butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride' 1, 2,3,4,5-cyclohexane tetra Carboxylic dianhydride, 3,3,,4,4 / dicyclohexyltetracarboxylic dianhydride, cis- 3,7-dibutylcyclooctane-1,5-diene-1,2,5,6 —tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarbonyl-2 residue-norbornane-2:3,,5:6-dianhydride , 2, 3, 4 This paper scale applies to China National Standard (CNS) A4 specification (21〇Χ297 mm) ' (Please read the note on the back and fill out this page) 4.

經濟部智慧財產局員工消費合作社印製 1299057 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（5 ) ，5 —四氫呋喃羧酸二酐，1 ，3 ，3 a ，4，5 ，9b —六氯一 5 — （四氯一 2 ，5 — —氧一 3 —咲喃基）一萘 〔1 ，2 — c〕—咲喃 1 ，3 —二酮，1 ，3，3a ，4 ，5 ，9b —六氨一5 —甲基一5 —(四氨一2 ，5 ——> 氧一 3 — 11夫喃基）一蔡〔1 ，2 — c〕— 13夫喃一 1 ，3- 二酮，1 ，3 ，3 a ，4，5 ，9b —六氫—5 —乙基一 5 —（四氫一2 ，5 —二氧一3 —呋喃基）—萘〔1 ，2 —c〕—咲喃—1 ，3 —二酮，1 ，3，3a ，4，5， 9 b —六氯一 7 —甲基一 5 —(四氨一2 ，5 — —^氧一3 一呋喃基）—萘〔1 ，2 — c〕—呋喃一 1 ，3 -二酮， 1 ，3 ，3a ，4 ，5 ，9b —六氫一7 —乙基一5 —( 四氫—2 ，5 —二氧—3 —呋喃基〔1 ，2 — c〕—呋喃 —1 ，3 — —^嗣，1 ，3 ，3a ，4，5 ，9b —六氯一 8 —甲基一5—(四氯一2 ，5 —二氧—3 —咲喃基）= 萘〔1 ，2 — c〕一咲喃 一1 ，3 —二酮，1 ，3，3a ，4，5，9b —六氫一8 —乙基一5—(四氫一2，5 一二氧—3 —呋喃基）—萘〔1 ，2 — c〕—呋喃—1 ， 3 —二嗣，1 ，3 ，3a ，4，5 ，9b —六氯一5 ，8 —一甲基一5 —(四氯一2 ，5 — •氧一3 —卩夫π南基）一 萘〔1 ，2 — c〕—呋喃—1 ，3 —二酮，5— (2，5 —二氧四氫呋喃基）—3 —甲基—3 —環己烯—1 ，2 — 二羧酸二酐，雙環〔2 · 2 · 2〕—辛—7 —烯一 2，3 ，5，6 -四羧酸二酐，下式（3 )及（4 )所表化合物 等脂族及脂環式四羧酸二酐； 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 1299057, Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing A7 B7 V. Inventions (5), 5 - Tetrahydrofurancarboxylic dianhydride, 1, 3, 3 a, 4, 5 9b - hexachloro-5-(tetrachloro-2,5-oxy-3-pyranyl)-naphthalene[1,2-c]-purine 1,3-dione, 1, 3, 3a, 4 , 5 , 9b - hexaamine - 5 - methyl - 5 - (tetraamyl - 2 , 5 - > oxygen - 3 - 11 - fluoranyl) - a Cai [1, 2 - c] - 13 Fuan 1 , 3-dione, 1, 3, 3 a, 4, 5, 9b - hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1, 2 —c]—咲 ——1,3—dione, 1, 3, 3a, 4, 5, 9 b —hexachloro-7-methyl-5—(tetraamyl-1,5--oxygen 3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1 ,3 ,3a ,4 ,5 ,9b —hexahydro-7-ethyl-5 —(tetrahydro- 2,5-Dioxy-3-furyl-[1,2-c]-furan-1,3--^嗣,1,3,3a 4,5,9b—hexachloro-8-methyl-5-(tetrachloro-2,5-dioxy-3-pyranyl)=naphthalene [1,2—c]-pyranyl-1,3 — Diketone, 1, 3, 3a, 4, 5, 9b - hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c] —furan—1,3—biquinone, 1, 3, 3a, 4, 5, 9b—hexachloro-5,8-monomethyl-5—(tetrachloro-2,5—oxygen-3) π南基)-naphthalene [1,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1 —Dicarboxylic dianhydride, bicyclo[2 · 2 · 2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, the following compounds of formula (3) and (4) Family and alicyclic tetracarboxylic dianhydride; This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill out this page)

1299057 A7 B7 五、發明説明（6 ) Ο Π1299057 A7 B7 V. INSTRUCTIONS (6) Ο Π

(3)(3)

⑷ (請先閲讀背面之注意事項再填寫本頁) 衣 (式中，R3及R5示具芳環之2價有機基，R4及R6示 氫原子或烷基，多數存在之R4及R6可各相同或不同。 ) 苯均四酸二酐，3 ，，4，一二苯甲酮四羧 酸二酐，3 ，3 /，4，4 / 一聯苯碾四羧酸二酐，1 ， 3 ，4，8 —萘四羧酸二酐，2，3 ，6，7 —萘四羧酸 二酐，3 ，3 /，4，4 / —聯苯醚四羧酸二酐，3 ， 3 /，4，4 / —二甲基二苯基矽烷四羧酸二酐，3 ， 3 / ，4，4 / —四苯基矽烷四羧酸二酐，1 ，2 ，3 ， 4 一呋喃四羧酸二酐，4，4 / 一雙（3 ，4 —二羧基苯 氧基）二苯基硫醚二酐，4，4 > —雙（3，4 一二羧基 苯氧基）二苯基硕二酐，4，4〃 —雙（3，4 —二羧基 苯氧基）二苯基丙烷二酐，3，3 /，4，4/ —全氟異 伸丙基二酞酸二酐，3，，4，4/ —二苯基四羧酸 、11 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9- 二酐，對伸苯基一雙（三苯 (三苯基酞酸）二酐，雙（ 苯醚二酐，雙（三苯基酞酸 1299057 A7 __^B7 五、發明説明（7 ) 二酐，雙（酞酸）苯基膦化氧 基酞酸）二酐，鄰伸苯基一雙 三苯基酞酸）〜4，4 / 一二 )一 4，4 〜二苯醚二酐，雙（三苯基酞酸）一 4， 4/ 一二苯基甲烷二酐，乙二醇一雙（脫水三苯六甲酸酯 )’丙二醇一雙（脫水三苯六甲酸酯），1 ，4 一 丁二醇 一雙（脫水二苯六甲酸酯），1 ，6 -己二醇一雙（脫水 二本六甲酸鹽）’ 1 ，8-辛二醇一雙（脫水三苯六甲酸 鹽），2，2〜雙（4 一羥基苯基）丙烷一雙（脫水三苯 六甲酸酯），下式（5 )至（8 )所表之化合物等之芳族 四羧酸二酐。這些可以一種單獨或二種以上組合使用。 (請先閱讀背面之注意事項再填寫本頁)(4) (Please read the precautions on the back and fill out this page). (In the formula, R3 and R5 show a divalent organic group with an aromatic ring, R4 and R6 represent a hydrogen atom or an alkyl group, and most of the R4 and R6 may exist. Same or different.) Pyromellitic dianhydride, 3,4, benzophenone tetracarboxylic dianhydride, 3,3 /, 4,4 / biphenyl hydride tetracarboxylic dianhydride, 1, 3 , 4,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 /,4,4 /diphenyl ether tetracarboxylic dianhydride, 3, 3 / , 4,4 / - dimethyldiphenyl decane tetracarboxylic dianhydride, 3, 3 / , 4, 4 / - tetraphenyl decane tetracarboxylic dianhydride, 1, 2, 3, 4 - furan tetracarboxylic acid Acid dianhydride, 4,4 / bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4 >-bis(3,4-dicarboxyphenoxy)diphenyl Resin, 4,4〃-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3 /,4,4/-perfluoroisopropenyldicarbonate dianhydride, 3,4,4/-diphenyltetracarboxylic acid, 11 Ministry of Economic Affairs, Intellectual Property Office, employee consumption cooperative, printed paper scale applicable to China Household Standard (CNS) A4 Specification (210X297 mm) -9- dianhydride, p-phenylene-bis(triphenyl(triphenylphosphonate) dianhydride, bis(phenylene ether dianhydride, bis(triphenylphosphonium) Acid 1299057 A7 __^B7 V. Description of invention (7) dianhydride, bis(decanoic acid) phenylphosphineoxy phthalic acid) dianhydride, o-phenyl bis-triphenyl decanoic acid) ~4,4 / 1-2) 4,4~diphenyl ether dianhydride, bis(triphenylphosphonic acid)-4,4/diphenylmethane dianhydride, ethylene glycol-double (dehydrated triphenyl hexaformate) propylene glycol One pair (dehydrated triphenyl hexaformate), 1,4-butanediol-double (anhydrous dibenzoate), 1,6-hexanediol-double (anhydro-dihexacarboxylate)' 1 ,8 - octanediol-double (dehydrated triphenyl hexaformate), 2,2~bis(4-hydroxyphenyl)propane-double (anhydrotriphenyl hexaformate), the following formula (5) to (8) An aromatic tetracarboxylic dianhydride such as a compound. These may be used alone or in combination of two or more. (Please read the notes on the back and fill out this page)

訂 1299057 A7 B7 五、發明説明（8 )Order 1299057 A7 B7 V. Description of invention (8)

(請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 這些之中，丁烷四羧酸二酐，1 ，2 ，3 ，4 一環戊 烷四羧酸二酐，2，3 ，5 —三羧基環戊基醋酸二酐，5 一 （2 ，5 —二氧四氫呋喃基）一 3 —甲基一 3 —二環己 烷一 1 ，2 —二羧酸二酐，順式一 3 ，7 —二丁基環辛一 1，5—二烯—1，2，5，6—四羧酸二酐，3，5, 6 -三羰基—2 -羧基降冰片烷一 2 : 3，5 : 6 —二酐 ，1，3 ，3a ，4，5 ，9b —六氣—5—(四氣—2 ，5 —二氧—3 —咲喃基）—蔡〔1 ，2 — c〕咲喃—1 ，3 —二丽，1 ，3，3a ，4，5，9b —六氫—8 — 甲基—5 —(四氫—2，5 —二氧一 3 — D夫喃基）一萘〔 1 ，2 — c〕呋喃—1 ，3 —二酮，1 ，3，3 a ，4， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -11 - 1299057 A7 ___B7_ 五、發明説明（9 ) 5 ，9 b —六氫一8 —甲基一5 —(四氫一2 ，5 —二氧 一 3 —呋喃基）一萘〔1 ，2 — c〕呋喃—1 ，3 —二酮 ，雙環〔2 · 2 · 2〕一辛—7 —烯一 2，3，5，6 — 四羧酸二酐，苯均四酸二酐，3 ，3 / ，4，4< —二苯 甲酮四羧酸二酐，3 ，3 /，4 / 一二苯基碾四羧酸二酐 ，1 ，4，5 ，8 -萘四羧酸二酐，上述式（3)所表化 合物中之下述之（9 )至（1 1 )所表之化合物及上述式 (4 )所表化合物中下述式（1 2 )所表之化合物，因可 呈現良好的液晶定向性而爲較佳，特佳者則可舉1 ，2， 3 ，4 —環丁烷四羧酸二酐，1 ，3 —二甲基一 1 ，2， 3 ，4 —環丁烷四羧酸二酐，2 ，3，5 -三羧基環戊基 醋酸二酐，1，3，3a，4，5，9b —六氫- 5- ( 四氫一 2，5 — —氧—3—咲喃基）—萘〔1 ，2 - c〕 呋喃—1 ，3 -二酮，雙一 3 ，7 —二丁基環辛一 1 ，5 —二儲—1 ，2 ，5 ，6 —四殘酸二酐，3，5，6 -三 羰基一 2 —羧基降冰片烷—2 : 3，5 : 6 —二酐，1 ， 3 ，3a ，4 ’ 5 ，9b —六氫一8 —甲基—5—(四氫 —2，5 —二氧一 3 -呋喃基）一萘〔1 ，2 - c〕呋喃 —1，3 -二酮，苯均四酸二酐及下述式（9)所表之化 合物。 本紙張尺度適财關家標準(CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產局員工消費合作社印製 1299057 五、發明説明（10) A7 B7(Please read the notes on the back and fill out this page.) The Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed these, butane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentane tetracarboxylic dianhydride , 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-1,3-dicyclohexane-1,2-dicarboxylic dianhydride , cis- 3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane A 2:3,5:6-dianhydride, 1,3,3a,4,5,9b—six gas—5—(four gas—2,5-dioxo-3—anthranyl)—Cai [1 , 2 — c] 咲 — — 1, 3 — 2, 2, 3, 3a, 4, 5, 9b — hexahydro-8 — methyl — 5 — (tetrahydro-2,5-dioxy- 3 — D. fluorenyl)-naphthalene [1,2-c]furan-1,3-dione, 1, 3,3 a, 4, this paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) - 11 - 1299057 A7 ___B7_ V. Description of invention (9) 5 , 9 b - hexahydro-8 - methyl one 5 - ( Tetrahydro-2,5-dioxy-3-furanyl-naphthalene[1,2-c]furan-1,3-dione, bicyclo[2 · 2 · 2]-octyl-7-ene-2 3,5,6 —tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 / ,4,4<-benzophenone tetracarboxylic dianhydride, 3,3 /,4 / diphenyl a tetracarboxylic dianhydride, a 1,4,5,8-naphthalenetetracarboxylic dianhydride, a compound represented by the following formula (9) to (1 1 ) in the compound of the above formula (3), and the above formula (4) The compound represented by the following formula (1 2 ) in the above-mentioned compound is preferred because it exhibits good liquid crystal orientation, and particularly preferred is 1,2,3,4-cyclobutane IV. Carboxylic dianhydride, 1,3,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a ,4,5,9b—hexahydro-5-(tetrahydro-2,5-oxy-3-pyranyl)-naphthalene[1,2-c]furan-1,3-dione, double-3 ,7-dibutylcyclooctane-1,5-di-storage-1,2,5,6-tetraresidic acid dianhydride, 3,5,6-tricarbonyl-2-carboxylate Alkane-2: 3,5:6-dianhydride, 1, 3, 3a, 4' 5 , 9b - hexahydro-8-methyl-5-(tetrahydro-2,5-dioxy-3-furanyl a naphthalene [1,2 -c]furan-1,3-dione, pyromellitic dianhydride and a compound represented by the following formula (9). This paper scales the financial standard (CNS) A4 specification (210X297 mm) (please read the note on the back and fill out this page), 11 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1299057 V. Invention description (10 ) A7 B7

1299057 A7 B7 五、發明説明（11) 具苯二胺構造之化合物。 碳原子數4至4 0之脂環骨幹可舉例如，環丁烷，環 戊烷，環己烷，環癸烷等來自環烷之脂環骨幹；膽甾醇， 膽甾烷醇等之甾族骨幹；降冰片烯骨幹，金鋼烷骨幹等， 這些之中以甾族骨幹爲較佳。又，上述式（2 )中R 2所 表之具脂環骨幹的有機基，亦可係烴鹵素原子取代者。 又，上述式（2)中，X所表之2價有機基，可舉 一〇一，一 C〇〇一’一〇C〇一’ 一 NliCO — ’ —CONH —，一 C〇一，伸甲基，嫌基，伸苯基等。這 些之中’特佳者爲一〇一’ 一C〇〇一 ’一〇C〇一所表 之基。 特定二胺之具體例，較佳者可舉下式（1 3)至 (1 8 )所表示化合物。 經濟部智慧財產局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁)1299057 A7 B7 V. INSTRUCTIONS (11) Compounds with a phenylenediamine structure. The alicyclic backbone having 4 to 40 carbon atoms may, for example, be an alicyclic backbone derived from cycloalkane such as cyclobutane, cyclopentane, cyclohexane or cyclodecane; a steroid of cholesterol, cholesteryl or the like The backbone; the norbornene backbone, the rutile backbone, etc., among which the Yi backbone is preferred. Further, the organic group having an alicyclic backbone represented by R 2 in the above formula (2) may be a hydrocarbon halogen atom-substituted one. Further, in the above formula (2), the divalent organic group represented by X may be exemplified by one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one Methyl, suspicion, phenyl and the like. Among these, the 'excellent ones' are one-on-one, one C, one, one, one, and one. Specific examples of the specific diamine include compounds represented by the formulae (13) to (18). Printed by the Consumers' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs (please read the notes on the back and fill out this page)

準 標 家 國 國 i中 用 適 ▲ 尺 一張 紙 I釐 公 7 9 2 1299057 A7 B7 五、發明説明（12)Appropriate standard country i use appropriate ▲ ruler piece paper I PCT 7 9 2 1299057 A7 B7 V. Invention description (12)

zCH3 、CH3 (16) (18) (請先閲讀背面之注意事項再填寫本頁) 衣·zCH3, CH3 (16) (18) (Please read the notes on the back and fill out this page)

經濟部智慧財產局員工消費合作社印製 上述聚醯胺酸之合成中，在無損本發明之效果的程度 ，亦可倂用其它二胺化合物。其它二胺化合物可舉例如， 對苯二胺，鄰苯二胺，4，4 / 一二胺基二苯基甲烷，4 ，4 / 一二胺基二苯基乙烷，4，4 / 一二胺基二苯硫醚 ，4，4 / 一二胺基二苯硕，3 ，3 '—二甲基一4，4 本紙張尺度適用中國國家標準（CNS ) Μ規格（210X297公^ _ 15 一 1299057 A7 B7 五、發明説明（13) ——二胺基聯苯，4，4 / 一二胺基苯醯替苯胺，4，4 /一二胺基二苯醚，1 ，5 -二胺基萘，3 ，3 -二甲基 (請先閱讀背面之注意事項再填寫本頁) —4，4 / —二胺基聯苯，5 —胺基—1 — ( 4 — 一胺基 苯基）二1 ，3 ，3 —三甲基茚滿，6 —胺基一1— (4 胺基苯基）一 1 ，3 ，3 —三甲基茚滿，3 ，4/ — 二胺基二苯醚，3，3 / —二胺基二苯甲酮，3，4 / — 二胺基二苯甲酮，4，4 / —二胺基二苯甲酮，2 ，2-雙〔4 一胺基苯氧基〕苯基〕丙烷，2，2 -雙〔4 一（ 4 一胺基苯氧基）苯基〕六氟丙烷，2，2 -雙（4 一胺 基苯基）六氟丙烷，2，2 -雙〔4 一（4 一胺基苯氧基 )苯基〕硕，1 ，4 一雙〔4 一胺基苯氧基〕苯，1 ，3 一雙（4 一胺基苯氧基）苯，1 ，3 -雙（3 -胺基苯氧 基）苯，9 ，9 一雙（4 一胺基苯基）—10 -氫蒽，2 ，7 —二胺基芴，9 ，9 —雙（4 一胺基苯基）芴，4， 4> —伸甲基一雙（2 —氯苯胺），2，2/，5，5< —四氫—4，4，—二胺基聯苯，2 ，2·—二氯—4， 4 —二胺基一 5 ，5 —二甲氧基聯苯，3 ，3 — — 經濟部智慧財產局員X消費合作社印裝 伸 2 苯氟基化 異，} 三甲之 苯胺基 {氟表 對苯氧雙三所 彳雙苯 I I } I \)/ 基' 2 1—一 V 基甲 2 | οα 4 丙m， 基{ ， 伸三 2 胺至 4 異 | I I } ， 苯 2 基 4 9 苯間 I 胺 c 1 聯 { 基二 t C 基一胺 I 雙式 胺' -、 I 下 二 4 4 4' ， | ， C ， 4 苯； -4-4 聯胺 4 ， 4 ， 4 氟二 ， 胺ί 烷，八族 4 苯雙丙苯 D 芳 I 雙 I 氟聯基之 基 } ' 六 } 氧等 氧基 2 D基苯物 甲丙，基甲 } 合 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16 - 1299057 A7 B7 五、發明説明（14) CH3Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. In the synthesis of the above polyamic acid, other diamine compounds may be used to the extent that the effects of the present invention are not impaired. Other diamine compounds may, for example, be p-phenylenediamine, o-phenylenediamine, 4,4/diaminodiphenylmethane, 4,4/diaminodiphenylethane, 4,4/1 Diaminodiphenyl sulfide, 4,4 / diaminobiphenyl, 3,3 '-dimethyl-4,4 This paper scale applies to China National Standard (CNS) ΜSpecifications (210X297 public ^ _ 15 A 1299057 A7 B7 V. INSTRUCTIONS (13) ——Diaminobiphenyl, 4,4/diaminophenylbenzophenidine, 4,4/diaminodiphenyl ether, 1,5-diamine Naphthyl, 3,3-dimethyl (please read the notes on the back and fill out this page) —4,4 / —diaminobiphenyl, 5-amino- 1 — ( 4 — monoaminophenyl ) 2,3,3-trimethylindan, 6-amino-1-(4-aminophenyl)-1,3,3-trimethylindan, 3,4/-diaminodi Phenyl ether, 3,3 / -diaminobenzophenone, 3,4 / -diaminobenzophenone, 4,4 / -diaminobenzophenone, 2,2-double [4 Aminophenoxy]phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2, 2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl], 1,4-bis[4-aminophenoxy Benzene, 1,3, bis(4-aminophenoxy)benzene, 1,3 -bis(3-aminophenoxy)benzene, 9, 9-bis(4-aminophenyl)-10 -hydroquinone, 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4, 4>-methyl-bis(2-chloroaniline), 2,2/, 5,5<-tetrahydro-4,4,-diaminobiphenyl, 2,2·-dichloro-4,4-diamino- 5,5-dimethoxybiphenyl, 3,3 — — Ministry of Economic Affairs, Intellectual Property Officer, X Consumer Cooperative, Printing and Extrusion 2 Benzene Fluorylation,} Trimethylaniline {Fluorophene Benzene Oxygenate, Diphenyl II } I \)/ Base ' 2 1—One V Base A2 | οα 4 propyl m, yl { , exo 3 2 amine to 4 iso | II } , phenyl 2 yl 4 9 phenyl I amine c 1 联 { yl 2 t C yl 1 amine I diamine ' -, I under 2 4 4 4 ' , | , C , 4 benzene ; -4-4 hydrazine 4 , 4 , 4 fluorodi , amine aceane , octa 4 benzoic propyl D aryl I double I fluorinated Base} 'Six} Oxygen isotherm 2 D-based benzene-propyl, ketone} The paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -16 - 1299057 A7 B7 V. Description of invention ( 14) CH3

CH3 CH3 (19) CH3CH3 CH3 (19) CH3

CH3 CH3 (20) (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1 ，1 —間二甲苯二胺，1 ，3 —丙二胺，四伸甲基 二胺，五伸甲基二胺，六伸甲基二胺，七伸甲基二胺，八 伸甲基二胺，九伸甲基二胺，4，4 一二胺基七伸甲基二 胺，1 ，4 —二胺基環己環，異佛爾酮二胺，四氫雙環戊 二烯二胺，六氫—4，7 —四橋茚滿酮二伸甲基二胺，三 環〔6 · 2 · 1 · 02，7〕一伸十一基二甲基二胺，4 4 / 一伸甲基（環己基）等脂族及脂環式二胺； 2 ，3 —二胺基吡啶，3 ，4 —二胺基吡啶，2 ，4 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17^ 1299057 A7 B7 五、發明説明（15) 胺基嘧啶，5，6 —二胺基—2，3 —二氰基 6——二胺基一 2，4 一二羥基嘧啶，2，4 一 基胺基—1 ’ 3，5 —三畊，1 ，4 一 胺基一 6 -異丙氧基 —6 —二甲 胺基丙基）哌畊 吡哄， 二胺基 雙 5 5 -啡， 4 一二胺基 乙燦基一 s 三畊，2 2，4 一 一 1，3 —三畊， 2，4 一 ，4 —二 二胺基— ，5 —三 2 ， 4 一 胺基一 6 -苯基—1 6 甲基一 s —三哄 哄；4 ，6 二胺 6 -二胺基嘌呤，5 ’ 6〜二胺 一二胺基 -苯基噻唑 ，2 —2 5 一 1 2 胺基- 2 -乙氧基吖啶乳酸酯 *胺基呢 基氮雜菲 1 ， 4 一 哄， 式（ 有2 —級胺基 雙（4 -胺基苯基）苯胺及下 化合物等之，分子內 原子的二胺； 基一 5 基—1 4 一***，6 ，8 ~ 3 —二甲基尿 (請先閱讀背面之注意事項再填寫本頁) 3，62 2) 及該一 二胺基一 一二胺基 ，（2 3 級胺基以 9 一二 6 -苯 吖啶， )所表 外之氮 經濟部智慧財產局員工消費合作社印製CH3 CH3 (20) (Please read the note on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed 1,1 - meta-xylene diamine, 1,3-dipropylenediamine, tetramethyl Diamine, pentamethylamine, hexamethylenediamine, heptamethylamine, octamethylamine, hexamethylenediamine, 4,4 bisaminosolemethyl Amine, 1,4-diaminocyclohexyl ring, isophorone diamine, tetrahydrodicyclopentadiene diamine, hexahydro-4,7-tetra bridge indanone di-methyldiamine, tricyclic [6 · 2 · 1 · 02, 7] an extended eleven dimethyldiamine, 4 4 / a methyl (cyclohexyl) and other aliphatic and alicyclic diamines; 2,3-diaminopyridine, 3,4-diaminopyridine, 2,4 This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -17^ 1299057 A7 B7 V. Description of invention (15) Aminopyrimidine, 5,6 — Diamino- 2,3-dicyano 6-diamino- 2,4-dihydroxypyrimidine, 2,4-ylamino- 1 '3,5-three tillage, 1,4-amino group 6-isopropoxy 6-dimethylaminopropyl ) pipetidine pyridinium, diamine bis 5 5 - morphine, 4 - diamino ethoxylated s three tillage, 2 2, 4 -1, 1, 3 - three tillage, 2,4 one, 4 - two Amino-, 5-tris- 2, 4-monoamino- 6-phenyl-1 6 methyl-s-triazine; 4,6-diamine 6-diaminopurine, 5'-6-diamine-two Amino-phenylthiazole, 2 - 2 5 -1 2 -amino 2-ethoxy acyl lactate * Aminyl fluorene phenanthrene 1 , 4 - fluorene, formula (with 2 -amino group double (4-Aminophenyl)aniline and the lower compound, the diamine of the intramolecular atom; the base 5-yl-l 4-triazole, 6,8 ~ 3-dimethyl urine (please read the back of the note first) Please fill out this page again) 3,62 2) and the diamino-amino-diamine group, (2 3 amino group with 9-dihexa-benzopyridinium,) Printed by employee consumption cooperatives

H2N (22) (式中，R 7示具含選自吡啶 哄 ’呢1定及呃畊之氮原 子的環狀構造之一價有機基，X示二價有機_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1299057 A7 B7 五、發明説明（16) H2N—^H2N (22) (wherein R 7 is a one-valent organic group containing a cyclic structure selected from the group consisting of pyridinium and nitrogen atoms, and X is a divalent organic _ This paper scale applies to Chinese national standards (CNS) A4 size (210X297 mm) 1299057 A7 B7 V. Description of invention (16) H2N—^

r* Ο- ΝΗ2 (23) (式中’ R示具含選自吡啶，嘧啶，三畊，哌啶及哌畊 之氮原子之環狀構造之二價有機基，X示二價有機基，多 數個存在之X，可係相同或不同。） 下式（2 4 )所表之二胺基有機矽氮烷； 經濟部智慧財產局員工消費合作社印製r* Ο- ΝΗ2 (23) (wherein R represents a divalent organic group having a cyclic structure selected from a nitrogen atom selected from the group consisting of pyridine, pyrimidine, tri-till, piperidine and piperazine, and X represents a divalent organic group, Most of the existing Xs may be the same or different.) The diamine-based organic decazins of the following formula (2 4 ); printed by the Intellectual Property Office of the Ministry of Economic Affairs

(請先閲讀背面之注意事項再填寫本頁) 衣. 訂(Please read the notes on the back and fill out this page.) Clothing. Order

本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -19 - Ϊ299057 苯 烷 4 苯2 3 胺 )2 發明説明（17) 7〜二胺基芴，4， 胺基苯氧 芴，2， 烷，2 ， 4 4-(4- 月女基苯基） 基〕六氟丙 一二胺基二苯醚，2，2 基）苯基〕丙烷，9，9一雙 2 —雙〔4 一（ 4 —胺 2 -雙（4 一胺基苯基 基）雙苯胺，1 〜月女，4 ’ 4 一伸 〜胺基苯氧 ’上述式（ 5 )，（ 2 ’ 4 -二胺 基B定，上 所表之化合 8 )所表之 基）苯， 1 9 )至 6 )所表 基吡啶， 述式（2 物及上述 化合物。 異伸丙 甲基雙 4，4 (21 之化合 2，4 2 )所 式（2 (環己胺），1 基苯氧 )六氟 ，4 一 ，4 一 一（4一胺基苯氧基 )所表之化合物，上述 物，2，6 -二胺基吡 一二胺基 表示之化 3 )所表 喃d定， 合物中 之化合 下式（ 物中下 一雙 (4 基） 丙烷 環己 雙（ )聯 式（ 啶， 2 7 式（ (請先閲讀背面之注意事項再填寫本頁} 訂- COO—CH2CH2This paper scale applies to Chinese National Standard (CNS) Α4 specification (210X297 mm) -19 - Ϊ299057 phenylene 4 benzene 2 3 amine) 2 Description of invention (17) 7~Diamino hydrazine, 4, Aminophenoxy oxime, 2, alkane, 2, 4 4-(4-month-female-phenyl)yl]hexafluoropropanediamine-diphenyl ether, 2,2-yl)phenyl]propane, 9,9-double 2-double 4 one (4 -amine 2 -bis(4-aminophenyl)diphenylamine, 1 ~ month female, 4 '4 a stretch of ~aminophenoxy" above formula (5), (2'4-diamino B, the compound shown in the above table 8)) benzene, 1 9 ) to 6) of the pyridine, the formula (2 and the above compound. Isopropyl propylene double 4, 4 (21 combination 2,4 2 ) a compound of the formula (2 (cyclohexylamine), 1 phenylphenoxy) hexafluoro, 4 -, 4 -1 (4-aminophenoxy), the above, 2, 6 - The diaminopyridyldiamine group represents a compound of 3), and the compound of the formula is the following formula (the next bis(4-yl)propane cyclohexyl( ) complex (pyridine, 2 7 formula) ((Please read the notes on the back and fill out this page again) Order - COO —CH2CH2

輕濟部智慧財產局員工消費合作社印製 本發明之液晶定向劑所含全部聚合體的全部二胺成分 中特定二胺所占比率，相對於二胺成分總量，以在1 0莫 耳％以上爲佳，2 0莫耳％以上爲更佳。該比率不足1 〇 莫耳％時，可能得不到充分之垂直定向效果。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） · 20 一 1299057 A7 B7 五、發明説明（18) 〔聚醯胺酸之合成〕 供合成聚醯胺酸之反應的四羧酸二酐及二胺之使用比 例，係以相對於二胺之胺基1當量，四羧酸二酐之酐基在 〇 · 2至2當量之比例爲佳，0 · 3至1 · 2當量之比例 則更佳。 聚醯胺酸之合成反應，在有機溶劑中，溫度條件通常 係一 2 0 °C至1 5 0 °C，以0至10 0艽爲較佳。在此， 有機溶劑僅須能溶解聚醯胺酸即無特殊限制，可例示如， 1 一甲基一2 —吡咯烷酮，N，N —二甲基乙醯胺，N， N —二甲基甲醯胺，二甲亞硕，丁內酯，四甲基尿素 ’六甲基磷醯三胺等之非質子系極性溶劑；間甲酚，二甲 酚，酚，鹵化酚等酚系溶劑。又，有機溶劑之使用量（α )，通常係，四羧酸二酐及二胺化合物之總量（/3 )爲， 相對於反應溶液之全量（α + /3 )，以在0 · 1至3 0重 量％爲佳。 而，上述有機溶劑，在生成之聚醯胺酸不析出之範圍 內，可以倂用聚醯胺酸之弱溶劑醇類，酮類，酯類，醚類 ，鹵化烴類，烴類等。此等弱溶劑之具體例可舉甲醇，乙 醇，異丙醇，環己醇，4 —羥基一 4 一甲基一 2 -戊酮， 乙二醇，丙二醇，1，4 — 丁二醇，三乙二醇，乙二醇單 甲醚，乳酸乙酯，乳酸丁酯，丙酮，甲乙酮，甲基異丁基 甲酮，環己酮，醋酸甲酯，醋酸乙酯，醋酸丁酯，甲基甲 氧基丙酸酯，乙基乙氧基丙酸酯，草酸二乙酯，丙二酸二 乙酯，丙二酸二乙酯，二***，乙二醇甲醚，乙二醇*** (請先閱讀背面之注意事項再填寫本頁) 衣·The Ministry of Intellectual Property of the Ministry of Light, Ministry of Commerce, and the Consumer Cooperatives printed the ratio of the specific diamine in the total diamine component of all the polymers contained in the liquid crystal aligning agent of the present invention, at 10% by mole relative to the total amount of the diamine component. The above is better, and more than 20% by mole is more preferable. When the ratio is less than 1 莫 mole %, sufficient vertical orientation may not be obtained. This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) · 20-1259057 A7 B7 V. Description of invention (18) [Synthesis of polyaminic acid] Tetracarboxylic acid for the synthesis of polylysine The ratio of the dianhydride and the diamine to be used is 1 equivalent of the amine group of the diamine, and the anhydride group of the tetracarboxylic dianhydride is preferably 〇 2 to 2 equivalents, and the ratio of 0 to 3 to 1.2 equivalents. The ratio is better. The synthesis reaction of polylysine is preferably carried out in an organic solvent at a temperature of from 20 ° C to 150 ° C, preferably from 0 to 100 °. Here, the organic solvent is only required to be capable of dissolving the polyamic acid, and is not particularly limited, and examples thereof include, for example, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl group. An aprotic polar solvent such as guanamine, dimethyl sulfoxide, butyrolactone, tetramethyl urea 'hexamethylphosphonium triamine, etc.; a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. Further, the amount of the organic solvent used (α) is usually such that the total amount (/3) of the tetracarboxylic dianhydride and the diamine compound is, relative to the total amount of the reaction solution (α + /3 ), at 0 · 1 It is preferably up to 30% by weight. Further, in the above organic solvent, a weak solvent alcohol of poly-proline, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon or the like may be used insofar as the produced polyamine does not precipitate. Specific examples of such weak solvents include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, and the like. Ethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy Propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether (please read the back first) Note: Please fill out this page)

經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（ 210X297公釐） -21 - 1299057 經濟部智慧財產局員工消費合作社印製 A7 _ B7五、發明説明（19) ’乙二醇正丙醚，乙二醇異丙醚，乙二醇正丁醚，乙二醇 二甲醚，乙二醇***醋酸酯，二乙二醇二甲醚，二乙二醇 二***，二乙二醇單甲醚，二乙二醇單***，二乙二醇二 ***，二乙二醇單甲醚，二乙二醇單***，二乙二醇單甲 醚醋酸酯，二乙二醇單***醋酸酯，四氫呋喃，二氯甲烷 ，1 ，2 —二氯乙烷，1 ，4 —二氯丁烷，三氯乙烷，氯 化苯，鄰二氯苯，己烷，庚烷，辛烷，苯，甲苯，二甲苯 等。 如上，可得溶解聚醯胺酸而成之反應溶液。然後，將 該反應溶液注入大量弱溶劑中得析出物，該析出物於減壓 下乾燥可得聚醯胺酸。又，將該聚醯胺酸再度溶解於有機 溶劑，再以弱溶劑析出，這些步驟進行一回或數回後可將 聚醯胺酸純化。 〔醯亞胺化聚合物之合成〕 構成本發明之液晶定向劑的醯亞胺化聚合物，可使上 述聚醯胺酸脫水閉環而合成。聚醯胺酸之脫水閉環可用， (i )將聚醯胺酸加熱之方法，或（i i )將聚醯胺酸溶 解於有機溶劑，於該溶液中添加脫水劑及脫水閉環觸媒， 並於必要時加熱之方法進行。又，本發明所用之醯亞胺化 聚合物，亦可含經部份脫水閉環，醯亞胺化率（聚合物全 部重複單元中，形成醯亞胺環之重複單元的比率以％表示 者）不足1 0 0 %之醯亞胺化聚合物。 上述（1 )之將聚醯胺酸加熱之方法中，反應溫度通 ^紙張尺度適用中國國家標準（口~5)八4規格（210父297公釐） -22 - (請先閲讀背面之注意事項再填寫本頁) 衣· 訂Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printed Paper Scale Applicable to China National Standard (CNS) Α4 Specification (210X297 mm) -21 - 1299057 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 _ B7 V. Invention Description (19 'Ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene Alcohol monoethyl acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorinated benzene, o-dichlorobenzene, hexane, heptane, Octane, benzene, toluene, xylene, and the like. As described above, a reaction solution in which polylysine is dissolved can be obtained. Then, the reaction solution is poured into a large amount of a weak solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. Further, the polyamic acid is dissolved again in an organic solvent and then precipitated as a weak solvent. The polyamine acid can be purified after one or several times of these steps. [Synthesis of ruthenium iodide polymer] The ruthenium iodide polymer constituting the liquid crystal aligning agent of the present invention can be synthesized by dehydration ring closure of the above polyglycolic acid. The dehydration ring of polylysine can be used, (i) heating the poly-proline, or (ii) dissolving the poly-proline in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and It is carried out by heating if necessary. Further, the ruthenium iodide polymer used in the present invention may further contain a partial dehydration ring closure, and the ruthenium imidization ratio (the ratio of the repeating unit forming the quinone ring in all repeating units of the polymer expressed by %) Less than 100% of the imidized polymer. In the above method (1), the method of heating the poly-proline is carried out, and the reaction temperature is applied to the Chinese national standard (mouth ~ 5) eight 4 specifications (210 parent 297 mm) -22 - (please read the back note first) Please fill out this page again.

1299057 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（20) 常係在5 0至2 0 0 °C，以6 0至1 7 0 °C爲佳。反應溫 度不足5 0 °C，則脫水閉環反應無法充分進行’而若反應 溫度超過2 0 0 °C，則所得聚醯胺酸（B )分子量可能低 落。 另一方面，上述（i i )之於聚醯胺酸溶液中添加脫 水劑及脫水閉環觸媒之方法中，脫水劑可用例如’醋酐’ 丙酸酐，三氟醋酐等酸酐。脫水劑之用量’取決於所欲之 醯亞胺化率，通常係以相對於聚醯胺酸之重複單元1莫耳 ，在0 . 0 1至2 0莫耳爲佳。又，脫水閉環觸媒可用例 如，吡啶，可力丁，二甲基吡啶，三乙胺等之三級胺。但 是，並非僅限於此。脫水閉環觸媒之用量，以相對於所用 之脫水劑1莫耳，在0 · 0 1至1 0莫耳爲佳。醯亞胺化 率可隨脫水劑，脫水閉環劑之增多而提高。從印刷性之觀 點，醯亞胺化率係以在7 0 %以下爲佳。而，用於脫水閉 環反應之有機溶劑，可舉例示爲聚醯胺酸之合成所用者之 有機溶劑。而脫水閉環之反應溫度通常係在0至1 8 0 °C ，較佳者爲1 0至1 5 0 t。又，對如此而得之反應溶液 ，可藉與聚醯胺酸之純化相同之方法，將醯亞胺化聚合物 純化。 〔末端修飾型聚合物〕 聚醯胺酸及醯亞胺化聚合物，亦可係分子量經調節之 末端修飾型者。藉該末端修飾型聚合物之使用，可無損本 發明之效果而改善液晶定向劑之塗布特性等。此類末端修 1紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -23: (請先閲讀背面之注意事項再填寫本頁) 衣· 訂1299057 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 5, invention description (20) is usually at 50 to 200 °C, preferably 60 to 170 °C. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction may not proceed sufficiently. If the reaction temperature exceeds 200 °C, the molecular weight of the obtained polyamic acid (B) may be lowered. On the other hand, in the above method (i i ) in which a dehydrating agent and a dehydration ring-closing catalyst are added to the polyaminic acid solution, an acid anhydride such as 'acetic anhydride' propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent' depends on the desired imidization ratio, and is usually in the range of from 0.01 to 20 moles per mole of the repeating unit of the poly-proline. Further, the dehydration ring-closing catalyst can be, for example, a tertiary amine such as pyridine, collidine, lutidine or triethylamine. However, it is not limited to this. The amount of the dehydration ring-closing catalyst is preferably from 0. 01 to 10 m with respect to 1 mol of the dehydrating agent used. The rate of hydrazine imidation can be increased with the increase of dehydrating agent and dehydration ring-closing agent. From the viewpoint of printability, the ruthenium imidation ratio is preferably 70% or less. Further, the organic solvent used for the dehydration ring-closing reaction can be exemplified as an organic solvent used for the synthesis of poly-proline. The reaction temperature of the dehydration ring closure is usually from 0 to 180 ° C, preferably from 10 to 150 t. Further, for the reaction solution thus obtained, the ruthenium iodide polymer can be purified by the same method as the purification of polylysine. [End-Modified Polymer] Poly-proline and quinone-imidized polymers may also be end-modified with a molecular weight adjusted. By the use of the terminal-modified polymer, the coating properties and the like of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. This type of end repair 1 paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) -23: (Please read the note on the back and fill out this page)

1299057 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明（21) 飾型者可於合成聚醯胺酸之際於反應系添加單酐，單胺化 合物，單異氰酸酯化合物等而合成。在此，單酐可舉例如 ，馬來酐，酞酐，衣康酐，正癸基琥珀酐，正十二基琥拍 酐，正十四基琥珀酐，正十六基琥珀酐等。又，單胺化合 物可舉例如，苯胺，環己胺，正丁胺，正戊胺，正己胺， 正庚胺，正辛胺，正壬胺，正癸胺，正十一烷胺，正十二 院胺，正十三烷胺，正十四烷胺，正十五烷胺，正十六院 胺，正十七烷胺，正十八烷胺，正二十烷胺等。又，單異 氰酸酯化合物，可舉例如苯基異氰酸酯，萘基異氰酸酯等 〇 〔聚合物之對數粘度〕 如上製得之聚醯胺酸及醯亞胺化聚合物，其對數粘度 (7?ln)之値係以0 · 0 5至1 0公合/公克爲佳， 0.05至5公合/公克爲更佳。 本發明中之對數粘度（7? ln)之値，係用N -甲基— 2 -吡咯院酮爲溶劑，對濃度0 · 5公克/ 1 〇 〇毫升之 溶液於3 0 °C作粘度測定，依下式（i )求出。 ln_ 1 η (溶液流下時間/溶劑流下時間) . "7^合物之重量濃度) ") 〔液晶定向劑〕 本發明之液晶定向劑，通常係於有機溶劑中溶解含有 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -24 - (請先閱讀背面之注意事項再填寫本頁)1299057 Α7 Β7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (21) The formula can be synthesized in the reaction system by adding monoanhydride, monoamine compound, monoisocyanate compound, etc. in the synthesis of poly-proline. Here, the monoanhydride may, for example, be maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride or the like. Further, the monoamine compound may, for example, be aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and positive ten II compound amine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecane, n-heptadecaneamine, n-octadecylamine, n-icosylamine, and the like. Further, examples of the monoisocyanate compound include phenyl isocyanate, naphthyl isocyanate, and the like (logarithmic viscosity of the polymer). The polyglycolic acid and the quinone imidized polymer obtained as described above have a logarithmic viscosity (7?ln). The lanthanide is preferably 0. 05 to 10 com/g, and more preferably 0.05 to 5 com/g. The logarithmic viscosity (7? ln) in the present invention is determined by using N-methyl-2-pyrrolidone as a solvent for a solution having a concentration of 0 · 5 g / 1 〇〇 ml at 30 ° C for viscosity measurement. It is obtained according to the following formula (i). Ln_ 1 η (solution flow time / solvent flow time) "7^ compound weight concentration) ") [liquid crystal aligning agent] The liquid crystal aligning agent of the present invention is usually dissolved in an organic solvent to contain the paper scale. China National Standard (CNS) Α4 Specifications (210X297 mm) -24 - (Please read the notes on the back and fill out this page)

1299057 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（22) 上述聚醯胺酸及/或醯亞胺化聚合物而構成。 調製本發明的液晶定向劑時之溫度，通常爲0 °c至 2 0 0 t：，而以2 0 °C至6 0 °C爲佳。 構成本發明液晶定向劑的有機溶劑，可舉例示爲用於 聚醯胺酸之合成反應者的溶劑。又，亦可適當選擇倂用例 示爲可倂用於聚醯胺酸之合成反應的弱溶劑。這些之中係 以用1 一甲基一 2 —吡咯烷酮，表面張力在3 2達因/公 分以下之溶劑爲佳。表面張力在3 2達因/公分以下之溶 劑，可舉例如4 一羥基一 4 一甲基—2 —戊酮，乙二醇單 甲醚，乳酸丁酯，醋酸丁酯，甲基甲氧基丙酸酯，乙基乙 氧基丙酸酯，乙二醇甲醚，乙二醇***，乙二醇正丙醚， 乙二醇異丙醚，乙二醇正丁醚（丁基溶纖劑），乙二醇二 甲醚，乙二醇***醋酸酯，二乙二醇二甲醚，二乙二醇二 ***，二乙二醇單甲醚，二乙二醇單***，二乙二醇單甲 醚醋酸酯，二乙二醇單***醋酸酯等。 1 一甲基一 2 —吡咯烷酮與表面張力在3 2達因/公 分以下之溶劑的比率，係以1 -甲基- 2 -吡咯烷酮爲 2 0至6 0重量％，表面張力在3 2達因/公分以下之溶 劑爲8 0至4 0重量％爲佳。在該比率範圍外時聚合物發 生析出，且流平性不足，故不得完美之印刷性。 本發明的液晶定向劑中之固體成分濃度係考量粘度， 揮發性等作選擇，而以在1至1 〇重量％之範圍爲佳。亦 即，本發明之液晶定向劑係塗布於基板表面形成液晶定向 膜之塗膜，當固體成分濃度不足1重量％時，該塗膜太薄 (請先閲讀背面之注意事項再填寫本頁) 衣.1299057 A7 B7 Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumer Cooperatives. V. Inventive Note (22) The above polylysine and/or ruthenium imidized polymer. The temperature at which the liquid crystal director of the present invention is prepared is usually from 0 ° C to 200 t: and preferably from 20 ° C to 60 ° C. The organic solvent constituting the liquid crystal aligning agent of the present invention can be exemplified as a solvent for a synthetic reactant of polyglycine. Further, a weak solvent which can be used for the synthesis reaction of poly-proline is also suitably selected. Among these, a solvent having a monomethyl-2-pyrrolidone and a surface tension of 3 2 dynes/cm or less is preferred. The solvent having a surface tension of 3 2 dynes/cm or less may, for example, be 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy group. Propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene Alcohol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate Ester, diethylene glycol monoethyl ether acetate, and the like. 1 The ratio of monomethyl-2-pyrrolidone to a solvent having a surface tension of 3 2 dynes/cm or less is 20 to 60% by weight of 1-methyl-2-pyrrolidone, and the surface tension is 3 2 dyne. The solvent of /min or less is preferably 80 to 40% by weight. When the ratio is out of the range, the polymer precipitates and the leveling property is insufficient, so that the printing property is not perfect. The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1 to 1% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate to form a coating film of the liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the coating film is too thin (please read the back of the back sheet and fill in the page) clothes.

、1T, 1T

本紙張尺度適用中國國家襟準（CNS ) A4規格（210X297公釐） 1299057 A7 B7 五、發明説明（23) 不得液晶定向膜，而當固體成分濃度超過1 0重量％時， 塗膜過厚不得良好之液晶定向膜，而且，液晶定向劑之粘 度增大塗布特性變差。 本發明之液晶定向劑，在無損於目標物性之範圍內， 爲提升對基板表面之粘著性，亦可含官能性矽烷化合物， 環氧化合物。有關之官能性矽烷化合物，可舉例如，3 -胺基丙基三甲氧基矽烷，3 -胺基丙基三乙氧基矽烷，2 -胺基丙基三甲氧基矽烷，2 -胺基丙基三乙氧基矽烷， N -（2 —胺基乙基）一 3 -胺基丙基三甲氧基矽烷，N 一（2 —胺基乙基）—3 —胺基丙基甲基二甲氧基矽烷， 3 —脲基丙基三甲氧基矽烷，3 —脲基丙基三乙氧基矽烷 ，N-乙氧基羰基一 3 —胺基丙基三甲氧基矽烷，N -乙 氧基羰基-3 —胺基丙基三乙氧基矽烷，N -三乙氧基砂 烷基丙基三乙三胺，N -三甲氧基矽烷基丙基三乙三胺， 10 —三甲氧基矽烷基一 1 ，4，7 —三吖癸烷，10 — 三乙氧基矽烷基一 1 ，4，7 —三吖癸烷，9 一三甲氧基 矽烷基—3，6 —二吖壬基醋酸酯，9 —三乙氧基矽烷基 —3 ，6 —二吖壬基醋酸酯，N —苯甲基一3 —胺基丙基 三甲氧基矽烷，N —苯甲基一 3 —胺基丙基三乙氧基矽院 ，N -苯基—3 -胺基丙基三甲氧基矽烷，N -苯基—3 一胺基丙基三乙氧基矽烷，N —雙（氧乙烯）一 3 —胺基 丙基三甲氧基矽院，N —雙（氧乙烯）一 3 —胺基丙基三 乙氧基矽烷等。有關之含環氧基之化合物，可舉例如，乙 二醇二環氧丙醚，聚乙二醇二環氧丙醚，丙二醇二環氧丙 (請先閱讀背面之注意事項再填寫本頁)This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1299057 A7 B7 V. Invention description (23) Liquid crystal orientation film is not allowed, and when the solid content concentration exceeds 10% by weight, the coating film is too thick. A good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent is increased to deteriorate the coating property. The liquid crystal aligning agent of the present invention may contain a functional decane compound or an epoxy compound in order to improve the adhesion to the surface of the substrate within a range not impairing the target physical properties. The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropane Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethyl Oxaloxane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-oxopropyltrimethoxydecane, N-ethoxylate Carbonyl-3-aminopropyltriethoxydecane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecane Base-1,4,7-trioxane, 10-triethoxydecyl-1,4,7-trioxane, 9-trimethoxydecyl- 3,6-didecyl Acetate, 9-triethoxydecyl- 3,6-dimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-amine Propyl triethoxy oxime, N-phenyl-3 Aminopropyltrimethoxydecane, N-phenyl-3-monoaminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyltrimethoxyphthalate, N-double ( Oxyethylene) 3-aminopropyltriethoxydecane, and the like. Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diepoxypropyl ester (please read the back sheet and read this page).

、1T, 1T

經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -26 - 1299057 A7 B7 五、發明説明（24) 醚，三丙二醇二環氧丙醚，聚丙二醇二環氧丙醚，新戊二 醇二環氧丙醚，1 ，6 —己二醇二環氧丙醚，甘油二環氧 (請先閲讀背面之注意事項再填寫本頁) 丙醚，2，2 -二溴新戊二醇二環氧丙醚’ 1 ’ 3 ’ 5 ’Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives Printed on this paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -26 - 1299057 A7 B7 V. Description of invention (24) Ether, tripropylene glycol diepoxypropyl Ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol epoxide (please read the back of the note before you fill out this page) Dipropyl ether, 2,2-dibromo neopentyl glycol diepoxypropyl ether ' 1 ' 3 ' 5 '

6 —四環氧丙基一 2 ，4 —己二醇，n，n,N N —四環氧丙基間二甲苯二胺，1 ，3 —雙（N，N 一二環 氧丙基胺基甲基）環己烷，N，N，一四環氧丙 基〜4，4 / —二胺基二苯基甲烷，3 一（N —烯丙基— N —環氧丙基）胺基丙基三甲氧基矽烷，3 —（N ’ N -二環氧丙基）胺基丙基三甲氧基砂院等。 〔液晶顯示元件〕 用本發明之液晶定向劑製得之液晶顯示元件’可依例 如，以下方法製造。 經濟部智慧財產局員X消費合作社印製 (1 )於設有圖案化之透明導電膜的基板之一面’以 例如輥塗法，旋塗法，印刷法等塗希本發明之液晶定向劑 ，再將塗布面加熱形成塗膜。於此’基板可用例如，浮法 玻璃，鈉玻璃等之玻璃；聚對苯二甲酸乙二醇酯，聚對苯 二甲酸丁二醇酯，聚醚碼，聚碳酸酯等之塑膠等透明基板 。設於基板之一面的透明導電膜可用氧化錫（S η〇2 ) 所成之NES Α膜（美國PPG公司註冊商標），氧化銦 一氧化錫（I n2〇3— Sn〇2)所成之I TO膜等，這 些透導電膜之圖案化，可用光刻法或使用預製遮罩之方法 。塗布液晶定向劑時爲使基板表面及透明導電膜與塗膜之 粘著性更爲良好，亦可於基板之該表面預先塗布官能性砂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -27 - 1299057 A7 B7 五、發明説明（25) (請先閱讀背面之注意事項再填寫本頁) 烷化合物，官能性鈦化合物等。塗布液晶定向劑後，加熱 溫度80至300 °C，以120至250。(：爲較佳。而， 含聚醯胺酸之本發明的液晶定向劑，係於塗布後去除有機 溶劑形成塗膜以爲定向膜，再經加熱進行脫水閉環，可成 進一步醯亞胺化之塗膜。形成的塗膜之厚度通常在 0 · 001至1微米，以0 · 005至〇 . 5微米爲佳。 (2 )將形成之塗膜面，以捲有例如尼龍，螺榮，棉 花等之纖維布料的輥筒於一定方向摩擦作平磨處理。藉此 ，於塗膜賦予液晶分子之定向能而成液晶定向膜。 又，於以本發明之液晶定向劑形成之液晶定向膜，如 例如日本專利特開平6 — 2 2 2 3 6 6號公報，特開平6 ——2 8 1 9 3 7號公報所示，以紫外線之部份照射作變化 傾角之處理，或如'' I D W 97 P 1 7 5 〃所記載之 方法，於同一面內形成電極之方法（I P S法），或如特 開平5 — 1 0 7 5 4 4號公報所示，於經平磨處理之液晶 定向膜表面，部份形成阻劑膜，於與先前不同之方向作平 磨處理後去除阻劑膜，利用施以變化液晶定向膜之液晶定 向能的處理，即可改善液晶顯示元件之視界特性。 經濟部智慧財產局員工消費合作社印製 (3 )製作2片如上形成液晶定向劑之基板，使各液 晶定向膜之平磨方向垂直或反平行，將2片基板隔著間隙 (單元間隙）相向配置，用封合劑將2片基板沿周圍貼合 ，將液晶定向劑注入充塡於基板表面及密封劑所區劃之單 元間隙內，將注入孔封合構成液晶單元。然後，於液晶單 元之外表面，亦即構成液晶單元的各基板之另一面將偏光 -28^ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1299057 A7 B7 五、發明説明（26) 板貼合，以使其偏光方向與形成於該基板的一面之液晶定 向膜的平磨方向一致或垂直，即得液晶顯示元件。 在此’密封劑可用例如，含硬化劑及作爲間隔物之氧 化鋁球之環氧樹脂等。 液晶可舉向列型液晶及層列型液晶，其中係以向列型 液晶爲佳，可用例如，席夫鹼系液晶，氧化偶氮系液晶， 聯苯系液晶’苯基環己院系液晶，酯系液晶，聯三苯系液 晶，聯苯環己烷系液晶，嘧啶系液晶，二噁烷系液晶，雙 環辛烷系液晶，庫班系液晶等。又，這些液晶亦可添加例 如’氯化膽甾，壬酸膽甾酯，碳酸膽甾酯等之膽固醇型液 晶及巾售商品名「C—15」「CB—15」（默克公司 製）之類的對掌劑等而使用。又再，亦可用雙二矽氧基苯 伸甲基對胺基一2 —甲基丁基肉桂酸酯等之強介電性液晶 〇 又，貼合於液晶單元外表面之偏光板可舉，將聚乙烯 醇一面延伸定向，一面吸收碘而成所謂Η膜之偏光膜，夾 以醋酸纖維素保護膜之偏光板，或僅以Η膜本身所成之偏 光板。 又，本發明之液晶定向劑適用於Μ V Α (多分域直向 )方式之液晶顯示元件。Μ V A方式係如「液晶Vol. 3 Νο·2117(1999年）」或特開平1 1 — 2 5 8 6 0 5所示， 使用凸起爲定向規定機制之垂直定向模式。凸起可各形成 於T F Τ基板側及彩色濾光片側，亦可於彩色濾光片側設 凸起，而於T F Τ側設隙縫。 本紙張尺度適用中蹢國家標準（CNS ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 衣· 訂 經濟部智慧財產局員工消費合作社印製 1299057 Α7 Β7 五、發明説明（27) 實施例 以下藉實施例更具體說明本發明，唯本發明並不限於 此等實施例。 〔聚合物之醯亞胺化率〕 聚合物於室溫減壓乾燥後，溶解於重氫化二甲亞硕， 以四甲基矽烷爲標準物質，於室溫測定1 Η — N M R，由 下式（i i )求出。 醯亞胺化率（％)二（l^Ai/AS α)χ 1〇〇 ( i i ) A1 :來自NH基之質子的高峰面積（1 〇 p pm) A2:來自其它質子之高峰面積 α :聚合物之前驅物（聚醯胺酸）中，相對於1個 ΝΗ基之質子，其它質子之個數比例 〔印刷性〕 用日寫「旺特洛碼」（日本寫真印刷公司製）印刷， 後烘焙後之基板以顯微鏡觀察。 無印刷不勻 〇6 —tetraepoxypropyl-2,4-hexanediol, n,n,NN—tetraepoxypropylm-xylylenediamine, 1,3—bis(N,N-diethylenepropylpropylamino) Methyl)cyclohexane, N,N,tetramethyloxypropyl~4,4/-diaminodiphenylmethane, 3-(N-allyl-N-epoxypropyl)aminopropyl Trimethoxy decane, 3-(N'N-diepoxypropyl)aminopropyltrimethoxy sand or the like. [Liquid Crystal Display Element] The liquid crystal display element 'made by the liquid crystal aligning agent of the present invention can be produced, for example, by the following method. Printed by the Ministry of Economic Affairs, the Intellectual Property Officer X Consumer Cooperative, (1) on the surface of one of the substrates provided with the patterned transparent conductive film, by, for example, roll coating, spin coating, printing, etc. The coated surface is heated to form a coating film. Here, the substrate may be, for example, a glass such as float glass or soda glass; a transparent substrate such as polyethylene terephthalate, polybutylene terephthalate, polyether or polycarbonate; . The transparent conductive film provided on one side of the substrate can be made of tin oxide (S η 〇 2 ) NES Α film (registered trademark of PPG, USA) and indium tin oxide (I n2 〇 3 - Sn 〇 2). I TO film, etc., the patterning of these conductive films can be performed by photolithography or by using a pre-mask. When the liquid crystal aligning agent is applied, the adhesion between the surface of the substrate and the transparent conductive film and the coating film is better, and the surface of the substrate may be pre-coated with the functional sandpaper. The Chinese National Standard (CNS) A4 specification (210X297) is applicable. PCT - -27 - 1299057 A7 B7 V. INSTRUCTIONS (25) (Please read the notes on the back and fill out this page) Alkane compounds, functional titanium compounds, etc. After coating the liquid crystal aligning agent, the heating temperature is 80 to 300 ° C to 120 to 250. (: is preferred. However, the liquid crystal aligning agent of the present invention containing poly-proline is obtained by removing the organic solvent after coating to form a coating film as an oriented film, and then performing dehydration ring closure by heating, thereby further yttrium-imiding Coating film. The thickness of the formed coating film is usually from 0. 001 to 1 micron, preferably from 0. 005 to 〇. 5 micrometers. (2) The coated film surface will be formed to be wound with, for example, nylon, rongrong, cotton. The roller of the fiber cloth is rubbed in a certain direction for flat grinding treatment, whereby the orientation of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Further, the liquid crystal alignment film formed by the liquid crystal aligning agent of the present invention, For example, as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 6-2 2 3 6 6 , which is disclosed in Japanese Laid-Open Patent Publication No. Hei. The method described in 97 P 1 7 5 〃, the method of forming an electrode in the same plane (IPS method), or the liquid crystal alignment film which is subjected to flat grinding as shown in Japanese Patent Laid-Open Publication No. Hei 5-1075 Surface, part of the formation of a resist film, in a different direction from the previous direction After removing the resist film and using the treatment of changing the liquid crystal orientation energy of the liquid crystal alignment film, the visual field characteristics of the liquid crystal display element can be improved. The Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative printing (3) making two pieces of the above liquid crystal The substrate of the directing agent is such that the flattening directions of the liquid crystal alignment films are perpendicular or anti-parallel, and the two substrates are disposed opposite to each other with a gap (cell gap), and the two substrates are bonded together by a sealing agent to inject the liquid crystal alignment agent. Filling the surface of the substrate and the cell gap partitioned by the sealant, sealing the injection hole to form a liquid crystal cell. Then, the outer surface of the liquid crystal cell, that is, the other surface of each substrate constituting the liquid crystal cell, will be polarized. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1299057 A7 B7 5. Inventive Note (26) The board is bonded so that its polarization direction and the flat direction of the liquid crystal alignment film formed on one side of the substrate Uniform or vertical, that is, a liquid crystal display element. Here, the 'sealant can be used, for example, an epoxy resin containing a hardener and an alumina ball as a spacer. Nematic liquid crystal and smectic liquid crystal, among which nematic liquid crystal is preferable, for example, Schiff base liquid crystal, oxidized azo liquid crystal, biphenyl liquid crystal 'phenyl ring system liquid crystal, ester type Liquid crystal, triphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, Kuban liquid crystal, etc. Further, these liquid crystals may also be added, for example, 'chlorinated bile甾, cholesteryl phthalate, cholesteryl carbonate and other cholesteric liquid crystals and towels sold under the trade name "C-15" "CB-15" (made by Merck) for use in palms, etc. It is also possible to use a strong dielectric liquid crystal such as bis-dimethoxy benzene to form methyl-p-amino-2-methylbutyl cinnamate, and a polarizing plate bonded to the outer surface of the liquid crystal cell, A polarizing film of a so-called enamel film, a polarizing plate sandwiched by a cellulose acetate protective film, or a polarizing plate formed only by the ruthenium film itself, in which the vinyl alcohol is extended and oriented. Further, the liquid crystal aligning agent of the present invention is suitable for a liquid crystal display element of a ΜV Α (multi-domain direct) method. Μ The V A mode is as shown in "Liquid Crystal Vol. 3 Νο·2117 (1999)" or Special Open 1 1 - 2 5 8 6 0 5 , and the vertical orientation mode in which the projection is a directional regulation mechanism is used. The bumps may be formed on the side of the T F Τ substrate and on the side of the color filter, or may be provided on the side of the color filter, and the slits may be provided on the side of the T F Τ. This paper size is applicable to China National Standard (CNS) Α4 specification (210X297 mm) (please read the note on the back and fill out this page). Clothing and Customs Ministry of Commerce Intellectual Property Bureau Staff Consumer Cooperative Printed 1299057 Α7 Β7 V. Invention DESCRIPTION OF THE INVENTION (Examples) Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited to the examples. [Polymerization rate of ruthenium of polymer] The polymer was dried under reduced pressure at room temperature, dissolved in dihydrogenated dimethyl sulfoxide, and tetramethyl decane was used as a standard substance. 1 Η-NMR was measured at room temperature. (ii) Find. Ruthenium amination rate (%) II (l^Ai/AS α)χ 1〇〇( ii ) A1 : Peak area of protons from NH group (1 〇p pm) A2: Peak area from other protons α : In the polymer precursor (poly-proline), the ratio of the number of other protons to the protons of one sulfhydryl group (printability) is printed by "Wentlot Code" (manufactured by Nippon Photo Printing Co., Ltd.). The substrate after post-baking was observed under a microscope. No uneven printing 〇

有印刷不勻 X 〔液晶顯示元件之製作方法〕 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -30 - (請先閲讀背面之注意事項再填寫本頁) Φ. 訂 經濟部智慧財產局員工消費合作社印製 1299057 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（28) 液晶顯示元件之製作（其1 ) ·· 於設置在厚度1毫米之基板的一面之I T 0膜所成之 透明導電膜上，用旋塗機塗布液晶定向劑，於8 0 t 1分 鐘再於1 8 0 °C 1小時乾燥，形成乾燥膜厚6 0 〇埃之塗 膜。 其次，用捲有嫘縈布之輥筒的平磨機作平磨處理，賦 予該薄膜液晶分子之定向能形成液晶定向膜。在此，平磨 處理條件係，輕筒轉速4 0 0 r p m，平台移動速度3 0 笔米/秒’看足擠入長度0·4¾米。 如上製作2片形成有液晶定向劑之基板，於各基板之 外緣部以網印法塗布含氧化鋁球之環氧樹脂系粘著劑後， 將2片基板隔著隔相向配置使平磨方向相反，外緣部互相 抵接壓合使粘著劑硬化。 由基板表面及外緣部之粘著劑所區劃出之單元間隙內 ’以負型向列型液晶注入充塡，再將注入孔以環氧系粘著 封合，製作垂直定向型液晶顯示元件（以下稱「液晶顯示 元件①」。 液晶顯示元件之製作（其2 ): 如第1圖所示，於具用正型阻劑形成之凸起的附有 I T〇之坡璃基板（A )及具I T〇圖案之玻璃基板（B )，各以液晶定向劑印刷，於8 0 °C 1分鐘再於1 8 0 °C 1小時乾燥，形成乾燥膜厚6 0 0埃之塗膜。 如上述製作2片形成有液晶定向劑之基板，於基板（ 本纸張尺度通用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)There is uneven printing X [How to make liquid crystal display elements] This paper size is applicable to China National Standard (CNS) Α4 specifications (210X297 mm) -30 - (Please read the notes on the back and fill out this page) Φ. Ministry of Intellectual Property Bureau employee consumption cooperative printed 1299057 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (28) Production of liquid crystal display device (1) ·· Set on the side of the substrate with a thickness of 1 mm On the transparent conductive film formed by the IT 0 film, the liquid crystal aligning agent was applied by a spin coater, and dried at 80 ° C for 1 hour at 180 ° C to form a coating film having a dry film thickness of 60 Å. Next, the flat grinding machine which rolls the roll of the cloth is used for the flat grinding process, and the orientation of the liquid crystal molecules of the film is imparted to form a liquid crystal alignment film. Here, the flat grinding conditions are as follows: the speed of the light cylinder is 4 0 0 r p m, and the speed of the platform moving is 3 0 m/s, which is enough to enter the length of 0·43⁄4 m. Two sheets of the substrate on which the liquid crystal aligning agent was formed were prepared as described above, and an epoxy resin-based adhesive containing alumina balls was applied by screen printing on the outer edge portions of the respective substrates, and then the two substrates were placed in the direction of the separator to make the flat grinding. In the opposite direction, the outer edge portions are pressed against each other to harden the adhesive. The negative-type nematic liquid crystal is injected into the cell gap which is defined by the adhesive on the surface of the substrate and the outer edge portion, and the injection hole is sealed by epoxy bonding to form a vertical alignment type liquid crystal display element. (hereinafter referred to as "liquid crystal display element 1". Production of liquid crystal display element (2): As shown in Fig. 1, a bumped glass substrate (A) with a positive resist formed by a positive resist is formed. And a glass substrate (B) having an IT 〇 pattern, each printed with a liquid crystal aligning agent, dried at 80 ° C for 1 minute and then at 180 ° C for 1 hour to form a coating film having a dry film thickness of 600 angstroms. Prepare two substrates with liquid crystal alignment agent as described above, and use the substrate (this paper size is generally Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back and fill in this page)

、ττ

1299057 A7 B7 五、發明説明（29) B )之外緣部以網印法塗布含粒徑3 .. 5微米之氧化鋁球 的環氧樹脂系粘著劑後，如第1圖之位置關係將2片基板 貼合。 由基板之表面及外緣部之粘著劑所區劃之單元間隙內 ’以默克公司製之負型液晶ML C 6 6 8 0注入充塡， 再以環氧系粘著劑封合注入孔製作垂直定向型液晶顯示元 件（以下稱「液晶顯示元件②」）。 〔預傾角〕 以中央精機公司製之〇M S — J 3 ，從2 5 °C之液晶的阻滯對稱角之滑移算出預傾角。 〔液晶顯示元件的電壓保持率〕 於液晶顯示元件以5伏特電壓，以6 0微秒之施加時 間，1 6 7毫秒之間隔施加後，測定施加解除1 6 7毫秒 後之電壓保持率。測定裝置係用東陽技術（股）製之 V H R - 1。 〔殘留D C電壓〕 於液晶顯示元件以重疊有直流1 · 〇伏特之3 0赫， 2 . 0伏特矩形波於7 0 °C之環境溫度施加1小時，緊接 在直流電壓切斷後之殘留於液晶單元內之電壓以閃爍消去 法測定，求出殘留D C電壓。 合成例1，2，4，5，比較合成例1及2 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂1299057 A7 B7 V. INSTRUCTION OF THE INVENTION (29) B) The epoxy resin-based adhesive containing an alumina ball having a particle size of 3 .. 5 μm is applied by screen printing at the outer edge portion, as shown in Fig. 1 Two substrates were bonded together. The cell gap scribed by the adhesive on the surface of the substrate and the outer edge portion is filled with a negative liquid crystal ML C 6 6 8 made by Merck, and the injection hole is sealed with an epoxy adhesive. A vertical alignment type liquid crystal display element (hereinafter referred to as "liquid crystal display element 2") is produced. [Pretilt angle] The pretilt angle was calculated from the slip of the symmetrical angle of the liquid crystal at 25 °C by 〇M S — J 3 by the company. [Voltage retention ratio of liquid crystal display element] After the liquid crystal display element was applied at a voltage of 5 volts at an application time of 60 microseconds at an interval of 167 msec, the voltage holding ratio after the release of 167 msec was measured. The measuring device was made up of V H R -1 manufactured by Dongyang Technology Co., Ltd. [Residual DC voltage] The liquid crystal display element is superimposed with a DC of 1 〇 volts, and a rectangular wave of 2.0 volts is applied at an ambient temperature of 70 ° C for 1 hour, and remains after the DC voltage is cut off. The voltage in the liquid crystal cell was measured by a scintillation erasing method to determine a residual DC voltage. Synthesis Example 1, 2, 4, 5, Comparative Synthesis Examples 1 and 2 This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill out this page)

經濟部智慧財產局員工消費合作社印製 1299057 A7 ^_______B7 五、發明説明（30) 於4 5 0公克之1 —甲基一2 —吡咯烷酮依序於添力口 二胺，四羧酸二酐，使表1所示之單體入料的固體成分濃 度成爲2 0重量％，於室溫反應4小時得聚醯胺酸。 合成例3 於合成例2之聚醯胺酸加入1 —甲基- 2 -吡咯烷酮 使固體成分濃度成爲5重量％之後，依表1之組成加入觸 媒，於8 0 °C進行脫水閉環反應4小時。再將該反應液注 入二***，沉澱，回收，乾燥，得醯亞胺化率2 0 %之聚 合物。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -33 - 1299057 A7 B7 五、發明説明（31) 經濟部智慧財產局員工消費合作社印製 表1 合成例 入料單體(莫耳％ ) 對數粘度 (公合/公克） 醯亞胺化觸媒 醯亞胺 化率 (%) 酸酐 二胺 吡啶/醋酐 1 CB(100) PDA(50) 式(13)之二胺 (50) 0.89 Μ J 0 2 CB(80) DMCB(20) PDA(75) 式(13)之二胺 (25) 0.76 Μ ^\\\ 0 3 CB(80) DMCB(20) PDA(75) 式(13)之二胺 (25) 0.76 1.0/1.0 20 4 CB(80) DMCB(20) PDA(75) 式(14)之二胺 (25) 0.70 Μ j \ w 0 5 CB(80) DMCB(20) 式(13)之二胺 (100) 0.65 Μ j \ \\ 0 比較合 成例1 DSDA(IOO) PDA(95) 式(13)之二胺 (5) 1.09 Μ j\\\ 0 2 CB(100) PDA(50) 正十八烷氧 基-1，4-二胺基 苯(50) 0.71 Μ j \ \\ 0 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -34 - 1299057 A7 B7 五、發明説明（32) CB : 1 ，2，3，4 一環丁烷四羧酸二酐 DMCB : 1 ，3 —二甲基一1 ，2 ，3 ’ 4 —環丁烷四 羧酸二酐 P D A :對苯二胺 D S d A :二苯硕四羧酸二酐 實施例1至5及比較例1 ，2 合成例中所得之聚合物溶於表2所示之溶劑後，經1 微米之濾材過濾調製液晶定向劑。用這些液晶定向劑製作 液晶顯不兀件。這些液晶定向劑及液晶顯示元件之評估結 果合倂示於表2。 (請先閱讀背面之注意事項再填寫本頁)Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed 1299057 A7 ^_______B7 V. Description of Invention (30) 1 to 50 gram of 1-methyl-2-pyrrolidone followed by Addition of Diamine, Tetracarboxylic Acid dianhydride, The solid content concentration of the monomer feed shown in Table 1 was changed to 20% by weight, and the mixture was reacted at room temperature for 4 hours to obtain poly-proline. Synthesis Example 3 After adding 1 -methyl-2-pyrrolidone to the polyglycine of Synthesis Example 2 to have a solid content concentration of 5% by weight, a catalyst was added according to the composition of Table 1, and a dehydration ring-closing reaction was carried out at 80 ° C. hour. Further, the reaction mixture was poured into diethyl ether, precipitated, recovered, and dried to obtain a polymer having a hydrazine imidation ratio of 20%. (Please read the notes on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210X297 mm) -33 - 1299057 A7 B7 V. Description of Invention (31) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Table 1 Synthesis Example Feeding Monomer (Mole %) Logarithmic Viscosity (Male/G) Rhodium Amination Catalyst Amination Rate (%) Anhydride II Aminopyridine/acetic anhydride 1 CB (100) PDA (50) Diamine of formula (13) (50) 0.89 Μ J 0 2 CB (80) DMCB (20) PDA (75) Diamine of formula (13) (25 0.76 Μ ^\\\ 0 3 CB(80) DMCB(20) PDA(75) Diamine (25) of formula (13) 0.76 1.0/1.0 20 4 CB(80) DMCB(20) PDA(75) (14) Diamine (25) 0.70 Μ j \ w 0 5 CB (80) DMCB (20) Diamine of formula (13) (100) 0.65 Μ j \ \\ 0 Comparative Synthesis Example 1 DSDA (IOO) PDA (95) Diamine of formula (13) (5) 1.09 Μ j\\\ 0 2 CB(100) PDA(50) n-octadecyloxy-1,4-diaminobenzene (50) 0.71 Μ j \ \\ 0 (Please read the note on the back and fill out this page) This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) ) -34 - 1299057 A7 B7 V. INSTRUCTIONS (32) CB : 1 , 2, 3, 4 -Cyclobutane tetracarboxylic dianhydride DMCB : 1 , 3 - dimethyl - 1 , 2 , 3 ' 4 - ring Butane tetracarboxylic dianhydride PDA: p-phenylenediamine DS d A : diphenyl terephthalic acid dianhydride Examples 1 to 5 and Comparative Examples 1 and 2 The polymer obtained in the synthesis example was dissolved in Table 2. After the solvent, the liquid crystal director was filtered through a 1 micron filter. These liquid crystal alignment agents are used to produce liquid crystal display elements. The evaluation results of these liquid crystal aligning agents and liquid crystal display elements are shown in Table 2. (Please read the notes on the back and fill out this page)

經濟部智慧財產局員工消費合作社印製 本紙張尺度通用中國國家標準（CNS ) A4規格（210 X 297公釐） -35 - 1299057Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. This paper scales the General Chinese National Standard (CNS) A4 specification (210 X 297 mm) -35 - 1299057

7 7 A B 五、發明説明（33) 表2 實施例 聚合體 溶劑(重量％) 印刷性 預傾角 (° ) 電壓保持 率(％) 殘留DC (毫伏） 1 合成例 1 1_甲基-2-吡咯烷酮(50) 丁 基溶纖劑(50) 〇 89.5 98.3 20 2 合成例 2 μ甲基-2-吡咯烷酮(50) 丁 基溶纖劑(50) 〇 89.5 98.5 20 3 合成例 3 1-甲基-2-吡咯烷酮(60) 丁基溶纖劑(40) 〇 89.7 98.6 10 4 合成例 4 1-甲基-2-吡咯烷酮(50) 丁基溶纖劑(50) 〇 89.4 98.8 20 5 合成例 5 1-甲基-2-吡咯烷酮(30) 丁 基溶纖劑(70) 〇 89.8 96.5 30 比較例 1 比較 合成例 1 1-甲基-2-吡咯烷酮(50) 丁 基溶纖劑(50) 〇 79.3 79.0 100 2 比較 合成例 2 μ甲基·2·吡咯烷酮(50) 丁基溶纖劑(50) X 89.6 98.0 20 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 實施例6至1 0，比較例3 合成例之聚合物溶於表3所示之溶劑後，以1微米之 濾材過濾調製液晶定向劑。用這些液晶定向劑，製作液晶 顯示元件②。這些液晶定向劑及液晶顯示元件之評估結果 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 36 _ 12990577 7 AB V. INSTRUCTIONS (33) Table 2 Example Polymer solvent (% by weight) Printability pretilt angle (°) Voltage retention (%) Residual DC (millivolt) 1 Synthesis Example 1 1_Methyl-2 - pyrrolidone (50) butyl cellosolve (50) 〇 89.5 98.3 20 2 Synthesis Example 2 μmethyl-2-pyrrolidone (50) butyl cellosolve (50) 〇 89.5 98.5 20 3 Synthesis Example 3 1-Methyl-2- Pyrrolidone (60) butyl cellosolve (40) 〇 89.7 98.6 10 4 Synthesis Example 4 1-Methyl-2-pyrrolidone (50) Butyl cellosolve (50) 〇 89.4 98.8 20 5 Synthesis Example 5 1-Methyl-2- Pyrrolidone (30) butyl cellosolve (70) 〇89.8 96.5 30 Comparative Example 1 Comparative Synthesis Example 1 1-Methyl-2-pyrrolidone (50) butyl cellosolve (50) 〇79.3 79.0 100 2 Comparative Synthesis Example 2 μMethyl ·2·Pyrrolidone (50) Butyl cellosolve (50) X 89.6 98.0 20 (Please read the note on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Examples 6 to 10, Comparative Example 3 After the polymer of the synthesis example was dissolved in the solvent shown in Table 3, the liquid crystal aligning agent was prepared by filtration through a filter medium of 1 μm. The liquid crystal display element 2 was produced using these liquid crystal aligning agents. Evaluation results of these liquid crystal alignment agents and liquid crystal display elements This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 36 _ 1299057

7 B 五、發明説明（34) 合倂示於表3。 經濟部智慧財產局員工消費合作杜印製 表3 實施 例 聚合物 溶劑（重量％ ) 電壓保持率 (% ) 殘留D C (毫伏） 6 合成例1 1 -甲基-2 -吡咯 烷酮（50) 丁基溶纖劑（50) 98.1 30 7 合成例2 卜甲基-2-D比咯 烷酮（50) 丁基溶纖劑（50) 98.3 30 8 合成例3 1 -甲基-2 -吡咯 烷酮（60) 丁基溶纖劑（40) 98.4 20 9 合成例4 1-甲基-2-D比咯 烷酮（50) 丁基溶纖劑（50) 98.6 40 10 合成例5 1-甲基-2-吼咯 烷酮（30) 丁基溶纖劑（70) 96.2 60 比較 例3 合成例6 1-甲基-2-吡咯 烷酮（50) 丁基溶纖劑（50) 97.8 190 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 37 - 1299057 A7 B7 五、發明説明（35) 圖面之簡單說明 第1圖本發明之實施例所用的Μ V A方式之液晶單元 的示意圖。 符號說明 1 彩色濾光片側電極（I τ〇） 2 液晶定向膜 3 像素電極（I T〇） 4 定向限制機制（凸起） 5 定向限制機制（隙縫） 6 液晶分子 發明效果 根據本發明可提供，製成液晶定向膜時，液晶之垂直 定向性良好，能形成高電壓保持特性，低殘像性，印刷性 優良之液晶定向膜，適用於垂直定向型液晶顯示元件之液 晶定向劑。 (請先閲讀背面之注意事項再填寫本頁) 衣· 訂7 B V. INSTRUCTIONS (34) The combination is shown in Table 3. Ministry of Economic Affairs Intellectual Property Bureau Staff Consumption Cooperation Duban Table 3 Example Polymer Solvent (% by weight) Voltage Retention (%) Residual DC (millivolt) 6 Synthesis Example 1 1 -Methyl-2-pyrrolidone (50) Butyl Solution Fibrous (50) 98.1 30 7 Synthesis Example 2 methyl-2-D pyrrolidone (50) butyl cellosolve (50) 98.3 30 8 Synthesis Example 3 1 -Methyl-2-pyrrolidone (60) butyl cellosolve ( 40) 98.4 20 9 Synthesis Example 4 1-Methyl-2-D pyrrolidone (50) Butyl cellosolve (50) 98.6 40 10 Synthesis Example 5 1-Methyl-2-pyrrolidone (30) Butyl solution Fibrous (70) 96.2 60 Comparative Example 3 Synthesis Example 6 1-Methyl-2-pyrrolidone (50) Butyl cellosolve (50) 97.8 190 (Please read the notes on the back and fill out this page) This paper size applies to China. National Standard (CNS) A4 Specification (210X297 mm) _ 37 - 1299057 A7 B7 V. DESCRIPTION OF THE INVENTION (35) BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a VA type liquid crystal cell used in an embodiment of the present invention. DESCRIPTION OF REFERENCE NUMERALS 1 color filter side electrode (I τ〇) 2 liquid crystal alignment film 3 pixel electrode (IT〇) 4 orientation restricting mechanism (bump) 5 orientation restricting mechanism (slit) 6 liquid crystal molecule effect of the invention according to the present invention When the liquid crystal alignment film is formed, the liquid crystal alignment film is excellent in vertical alignment property, and can form a liquid crystal alignment film having high voltage holding characteristics, low afterimage resistance, and excellent printability, and is suitable for a liquid crystal alignment agent of a vertical alignment type liquid crystal display element. (Please read the notes on the back and fill out this page)

經濟部智慧財產局員工消費合作社印製 -38- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）Printed by the Consumer Intellectual Property Office of the Ministry of Economic Affairs -38- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)

Claims (1)

12990 經濟部智慧財產局員工消費合作社印製 A8 B8 C8 D812990 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A8 B8 C8 D8 六、申請專利範圍 1 · 一種液晶定向劑，其特徵爲：含（A)下式（1) 【化1】Sixth, the scope of application for patents 1 · A liquid crystal aligning agent, which is characterized by: (A) Formula (1) [Chemical 1] 0 .· ·⑴ 在此’ R1係鹵素原子，碳原子數1至1 〇之烷基或碳原子 數1至10之氟化烷基，而a係〇至4之整數， 所示之四羧酸二酐與 (B)下述式（2) 【化2】0 .· (1) Here, 'R1 is a halogen atom, an alkyl group having 1 to 1 carbon atom or a fluorinated alkyl group having 1 to 10 carbon atoms, and a is 〇 to an integer of 4, and the tetracarboxylic acid is shown. Acid dianhydride and (B) the following formula (2) [Chemical 2] • ·⑵ 在此，X係2價有機基，R 2係具碳原子數4至4 0之脂環 骨架的1價有機基， 所示之二胺反應所生成之聚醯胺酸及該聚醯胺酸脫水閉環 生成之醯亞胺化聚合體之至少一種，以及 1 一甲基一 2 —吡咯烷酮2 0至6 0重量％及表面張 力在3 2達因/公分以下之其它溶劑8 0至4 0重量％者 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 1299057 A8 B8 C8 D8 申請專利範圍 如 第 圍 。 範件 利元 專示 請顯 申晶 液 型 向 定 直 劑 向 定 晶 液 之 項 垂 於 用 係 (請先閱讀背面之注意事項再填寫本頁) .夸. 訂• (2) Here, X is a divalent organic group, and R 2 is a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms, and the polyamine acid formed by the reaction of the diamine shown and the poly At least one of a ruthenium imidized polymer formed by dehydration of a proline, and 2 to 60% by weight of 1-methyl-2-pyrrolidone and 80% of other solvents having a surface tension of 3 2 dynes/cm or less 40% by weight This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the back note first and then fill out this page) 1299057 A8 B8 C8 D8 The scope of application is as follows. Fan Liyuan special instructions Please show the liquid crystal type to the straightening agent to the crystallization liquid item hanging on the system (please read the back of the precautions and then fill out this page). 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -40 -Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the consumer cooperatives. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -40 -