TW200831611A - Liquid crystal aligning agent and liquid crystal displays made by using the same - Google Patents
Liquid crystal aligning agent and liquid crystal displays made by using the same Download PDFInfo
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- TW200831611A TW200831611A TW096127599A TW96127599A TW200831611A TW 200831611 A TW200831611 A TW 200831611A TW 096127599 A TW096127599 A TW 096127599A TW 96127599 A TW96127599 A TW 96127599A TW 200831611 A TW200831611 A TW 200831611A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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- Nonlinear Science (AREA)
- Organic Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Liquid Crystal (AREA)
Abstract
Description
200831611 九、發明說明 【發明所屬之技術領域】 本發明係有關一種製作液晶配向膜時所使用的液晶配 向處理劑及使用其之液晶顯示元件。 【先前技術】 目前液晶顯示元件之液晶配向膜,主要係使用使聚醯 胺酸等之聚醯亞胺前驅體或可溶性聚醯亞胺之溶液爲主成 分的液晶配向處理劑(亦稱爲液晶配向劑)塗覆於玻璃基 板上予以燒成,稱爲聚醯亞胺系液晶配向膜。 液晶配向膜係以控制液晶之配向狀態爲目的所使用者 。然而’伴隨液晶顯币兀件之筒精細化,要求控制液晶顯 示元件之對比降低或減低殘像現象,故順序以其中所使用 的液晶配向膜中電壓保持率高,或施加直流電壓時之殘留 電荷少’及/或藉由直流電壓所囤積的殘留電荷之緩和作 用快速之特性爲重要。 於聚醯亞胺系液晶配向膜中,直至藉由直流電壓所產 生殘像消失的時間短者,係使用在聚醯胺酸或含醯亞胺基 之聚醯胺酸中加入含有特定構造之3級胺的液晶配向劑者 (例如參照專利文獻1 )、或使用以具有吡啶架構等之特 定二胺爲原料中所使用的含有可溶性聚醯亞胺的液晶配向 劑者(例如參照專利文獻2 )等,係爲已知。而且,電壓 保持率高、且直至藉由直流電壓所產生的殘像消失的時間 短者’係使用除聚醯胺酸或其醯亞胺化聚合物等外,含有 -6 - 200831611 極少量之選自在分子內含有1個羧酸基之化合物、在分子 內含有1個羧酸酐基之化合物及在分子內含有i個3級胺 基之化合物的液晶配向劑者(例如參照專利文獻3 ),係 爲已知。 然而,近年來大畫面、高精細的液晶電視廣爲實用化 ’該用途之液晶顯示元件,與直至目前以文字或靜止畫爲 主所顯示的顯示裝置用途相比時,對殘像之要求更爲嚴厲 ’且要求在嚴苛的使用環境下長期使用的耐久特性。因此 ’其中所使用的液晶配向膜必須較以往具有更高的信賴性 ,有關液晶配向膜之電氣特性,不僅要求初期特性良好, 且要求例如在高溫下長時間暴露後仍可維持良好的特性。 專利文獻1 :日本特開平9-3 1 6200號公報 專利文獻2:日本特開平10-1046 33號公報 專利文獻3 :日本特開平8 - 7 6 1 2 8號公報 【發明內容】 本發明係爲有鑑於上述情形者。換言之,本發明欲解 決的課題,係提供電壓保持率高、且即使在高溫下長時間 暴露後,仍可得藉由直流電壓所囤積的殘留電荷之緩和作 用快速的液晶配向膜之液晶配向處理劑。另外,提供一種 在嚴苛的使用環境下可耐長期使用、信賴性高的液晶顯示 元件。 本發明人等爲解決上述課題時,再三深入硏究的結果 發現藉由含有特定的聚醯亞胺及特定的胺化合物之液晶 200831611 配向處理劑,更詳言之,在有機溶劑中混合特定的聚醯亞 胺與特定的胺化合物所得的液晶配向處理劑,可解決上述 課題,遂而完成本發明。換言之,本發明具有以下述特徵 作爲要旨者。 (1 ) 一種液晶配向處理劑,其特徵爲含有下述(A ) 成分及(B )成分, (A) 成分:在分子內具有羧基之聚醯亞胺、 (B) 成分:在分子內具有1個一級胺基與含氮之芳香族 雜環,且該一級胺基鍵結於脂肪族烴基或非芳香族環式烴 基之胺化合物。 (2 )如(1 )記載之液晶配向處理劑,其中(A )成 分係爲使由以下述式〔1〕所示重複單位之構造式所成的 聚醯胺酸予以醯亞胺化的聚合物,該聚合物之羧基量對該 聚合物之重複單位而言平均値爲〇·1〜3個’ 〔化1〕[Technical Field] The present invention relates to a liquid crystal alignment treatment agent used in the production of a liquid crystal alignment film and a liquid crystal display element using the same. [Prior Art] At present, a liquid crystal alignment film of a liquid crystal display element mainly uses a liquid crystal alignment treatment agent (also referred to as liquid crystal) which is a solution of a polyamidene precursor such as polyacrylamide or a solution of soluble polyimine. The alignment agent is applied to a glass substrate and fired, and is called a polyimide film. The liquid crystal alignment film is intended for the purpose of controlling the alignment state of the liquid crystal. However, with the refinement of the cylinder of the liquid crystal display element, it is required to control the contrast of the liquid crystal display element to reduce or reduce the afterimage phenomenon, so the order is high in the liquid crystal alignment film used therein, or the residual voltage is applied. It is important that the charge is low and/or the relaxation of the residual charge accumulated by the DC voltage is fast. In the polyimine-based liquid crystal alignment film, the time until the disappearance of the afterimage due to the DC voltage is short, and the polyamine or the ruthenium-containing polyamine is added to the specific structure. A liquid crystal alignment agent containing a soluble polyimine (for example, refer to Patent Document 1) or a liquid crystal alignment agent containing a soluble polyimine which is used as a raw material for a specific diamine such as a pyridine structure (for example, refer to Patent Document 2) ), etc., is known. Further, the time when the voltage holding ratio is high and the afterimage until the disappearance of the afterimage due to the direct current voltage disappears is based on the use of a small amount of -6 - 200831611 except for polyacrylic acid or its ruthenium iodide polymer. a liquid crystal alignment agent selected from the group consisting of a compound containing one carboxylic acid group in the molecule, a compound containing one carboxylic acid anhydride group in the molecule, and a compound containing i tertiary amino groups in the molecule (for example, see Patent Document 3). The system is known. However, in recent years, large-screen, high-definition liquid crystal televisions have been widely used. The liquid crystal display elements of this type are more demanding for afterimages than the display devices that have been mainly displayed by characters or still pictures. Durable for long-term use in harsh environments. Therefore, the liquid crystal alignment film used therein must have higher reliability than the conventional one. Regarding the electrical characteristics of the liquid crystal alignment film, not only the initial characteristics are required to be good, but also good characteristics can be maintained, for example, after prolonged exposure at a high temperature. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. For those who have the above situation. In other words, the problem to be solved by the present invention is to provide a liquid crystal alignment treatment of a liquid crystal alignment film which has a high voltage holding ratio and can be quickly neutralized by a residual voltage accumulated by a DC voltage even after exposure for a long time at a high temperature. Agent. Further, it is possible to provide a liquid crystal display element which can withstand long-term use and has high reliability in a severe use environment. In order to solve the above problems, the inventors of the present invention have found that the liquid crystal 200831611 alignment treatment agent containing a specific polyimine and a specific amine compound is more specifically mixed in an organic solvent. The liquid crystal alignment treatment agent obtained by polyimine and a specific amine compound can solve the above problems, and the present invention has been completed. In other words, the present invention has the following features as the gist. (1) A liquid crystal alignment treatment agent comprising the following (A) component and (B) component, (A) component: a polyimine having a carboxyl group in a molecule, and (B) a component: having a molecule One primary amine group and a nitrogen-containing aromatic heterocyclic ring, and the primary amine group is bonded to an aliphatic hydrocarbon group or an amine compound of a non-aromatic cyclic hydrocarbon group. (2) The liquid crystal alignment treatment agent according to (1), wherein the component (A) is a polymerization in which the polyamic acid formed by the structural formula of the repeating unit represented by the following formula [1] is imidized. The amount of carboxyl groups of the polymer is 〇·1~3 '[1] for the repeating unit of the polymer.
[1] (式中,Ri係爲4價有機基,R2係爲2價有機基’ β係爲 正整數)。 (3 )如(1 )記載之液晶配向處理劑’其中(Α )成 分係爲使在以式〔1〕所示重複單位之構造式中’部分或 全部的重複單位爲具有以下述式〔2〕所示單位之構造式 -8-[1] (In the formula, Ri is a tetravalent organic group, and R2 is a divalent organic group 'β is a positive integer). (3) The liquid crystal alignment treatment agent according to (1), wherein the (Α) component is such that a part or all of the repeating unit in the structural formula of the repeating unit represented by the formula [1] has the following formula [2] 〕The structure of the unit shown-8-
200831611 所成的聚醯胺酸予以醯亞胺化的聚合物 量對該聚合物之重複單位而言平均値爲 〔化2〕200831611 The amount of polymer obtained by polyamidolic acid is imidized. The average amount of the repeating unit of the polymer is 化2.
(式中,R3係爲4價有機基,R4係爲 r4中至少一個具有羧基)。 (4 )如(1 )〜(3 )中任一項記 劑’其中(B)成分爲以下述式〔3〕所 〔化3〕 ’該聚合物之羧基 〇· 1〜3個, [2] 2價有機基,R3或 載之液晶配向處理 示之胺化合物, h2n(wherein R3 is a tetravalent organic group, and R4 is at least one of r4 having a carboxyl group). (4) The agent according to any one of (1) to (3) wherein the component (B) is a compound of the following formula [3], and the carboxyl group of the polymer is 1 to 3, [2] a divalent organic group, R3 or a liquid crystal alignment treatment of the amine compound, h2n
[3][3]
(式中’ X!係爲具有脂肪族烴基或非芙 價有機基,χ2係爲含氮之芳香族雜環) (5 )如(1 )〜(4 )中任一項記 劑’其中(B)成分爲以下述式〔4〕所 〔化4〕 h2n (式中,X3係爲碳數1〜1 〇之脂肪族尤 烴基,X4係爲單鍵、-〇-、-NH-、-S-、 之2價有機基,且χ3與χ4具有的碳1 :香族環式烴基之2 〇 載之液晶配向處理 示之胺化合物, [4] :基、非芳香族環式 •S〇2 -或碳數1〜19 (子之合計量爲1〜 -9- 200831611 20,X5係爲可具有取代基之含氮的芳香族雜環)。 (6 )如(5 )記載之液晶配向處理劑,其中(B )成 分係爲由式〔4〕之X3、X4及X5各選自下述記載之基或 環組合所成的胺化合物’ 其中,X3係爲1種選自碳數1〜1〇之直鏈或支鏈烷基 、碳數1〜1 〇之不飽和烷基、環丙烷環、環丁烷環、環戊 烷環、環己烷環、環庚烷環、環辛烷環、環壬烷環、環癸 烷環、環十一烷環、環十二烷環、環十三烷環、環十四烷 環、環十五烷環、環十六烷環、環十七烷環、環十八烷環 、環十九烷環、環二十烷環、三環二十烷環、三環二十二 烷環、二環庚院環、十氫萘環、原菠烷環、及金剛烷環所 成群者; X4係爲1種選自單鍵、-〇-、-NH-、-S-、-S02-、碳數1〜 19 之SX、-CO-0-、-〇-CO-、-CO-NH-、-NH-CO-、-CO-、-CF2-、-C ( CF3 ) 2-、-CH ( OH) -、-C ( CH3) 2-、 -Si ( CH3) 2-、-Ο-Si ( CH3 ) 2-、-Si ( CH3) 2-〇-、 -Ο-Si ( CH3 ) 2-0-、環丙烷環、環丁烷環、環戊烷環、環 己烷環、環庚烷環、環辛烷環、環壬烷環、環癸烷環、環 十一烷環、環十二烷環、環十三烷環、環十四烷環、環十 五烷環、環十六烷環、環十七烷環、環十八烷環、環十九 烷環、環二十烷環、三環二十烷環、三環二十二烷環、二 環庚烷環、十氫萘環、原菠烷環、金剛烷環、苯環、萘環 、四氫萘環、奠環、茚環、芴環、蒽環、菲環、菲那烯( Phenalene)環、吡咯環、咪哩環、噁哩環、噻π坐環、b比υ坐 200831611 環、吡啶環、嘧啶環、喹啉環、吡唑啉環、 唑環、嘌呤環、噻二唑環、噠嗪環、三嗪環 三唑環、吡嗪環、苯并咪唑環、間二氮茚環 菲繞啉環、吲哚環、喹喔啉環、苯并噻唑環 噁二唑環、吖啶環、噁唑環、哌嗪環、哌啶 及嗎啉環所成群者或數種組合所成的基; X5係爲1種選自吡咯環、咪唑環、螺π坐環、 環、吡啶環、嘧啶環、喹啉環、吡唑啉環、 唑環、嘌呤環、噻二唑環、噠嗪環、吡唑啉 吡唑烷環、三唑環、吡嗪環、苯并咪唑環、 帝I&琳ί哀、非繞琳環、卩引卩朵環、喹喔D林環、 吩噻嗪環、噁二唑環、吖啶環、及此等中任 取代基之基所成群者。 (7 )如(1 )〜(6 )中任一項記載之 劑,其中對1莫耳量(A )成分之聚醯亞胺 而言以0·01〜2莫耳倍量之比例含有(B )成 (8 )如(1)〜(7)中任一項記載之 劑’其中使(Α)成分之聚醯亞胺與(Β)成 在有機溶劑中進行加熱且混合、或混合後進 〇 (9 ) 一種液晶配向膜,其特徵爲由如 中任一項記載之液晶配向處理劑所得。 (1 0 ) —種液晶顯示元件,其特徵爲| 載之液晶配向膜。 異喹啉環、咔 、吡唑烷環、 、蒂諾啉環、 、吩噻嗪環、 環、二Β惡院環 噻唑環、吡唑 異喹啉環、咔 環、三嗪環、 間二氮茚環、 苯并噻唑環、 何一種可具有 液晶配向處理 中所含的羧基 分。 液晶配向處理 分的胺化合物 行加熱所得者 (1 )〜(8 ) I有如(9 )記 -11 - 200831611 〔發明之效果〕 本發明之液晶配向處理劑,可以較爲簡單的方法製得 。而且,本發明之液晶配向處理劑,電壓保持率高,且在 高溫下長時間暴露後仍可得藉由直流電壓所囤積的殘留電 荷之緩和作用快速的液晶配向膜。因此,具有由本發明之 液晶配向處理劑所得的液晶配向膜之液晶顯示元件,信賴 性優異,可適合利用於大畫面、高精細的液晶電視等。 〔爲實施發明之最佳形態〕 本發明之液晶配向處理劑,係爲含有(A )成分:在 分子內具有羧基之聚醯亞胺(以下亦稱爲特定聚醯亞胺) 、及(B )成分:在分子內具有1個一級胺基(-NH2 )與 含氮之芳香族雜環,且該一級胺基鍵結於脂肪族烴基或非 芳香族環式烴基之胺化合物(以下亦稱爲特定胺化合物) 之液晶配向處理劑。詳言之,係爲在有機溶劑中使(A ) 成分之特定聚醯亞胺、及(B )成分之特定胺化合物混合 所得的液晶配向處理劑。 於本說明書中,上述之胺基(-NH2 )係與1級胺基同 義,以下亦稱爲1級胺基。 於本發明之液晶配向處理劑中,可考慮爲特定胺化合 物中之1級胺基與特定聚醯亞胺中之羧基形成鹽,或對特 定聚醯亞胺中之羧基或羧基酯基而言,伴隨水或醇脫離、 進行醯胺鍵結,或對特定聚醯亞胺中之醯亞胺基而言,伴 -12- 200831611 隨醯亞胺基之開環、進行鍵結反 向膜時之燒成製程而定,可考慮 形成鹽的1級胺基,藉由水脫離 發明之液晶配向處理劑,與在有 無關,可考慮由其所得的液晶配 特定聚醯亞胺有效地鍵結之故。 另外,特定胺化合物中含氮 其共軛構造具有作爲電子跳動側 向膜中之電荷移動。而且,作爲 之芳香族雜環與特定聚醯亞胺中 結之靜電相互作用予以鍵結時, 基與特定的胺化合物中之含氮芳 作用。另外,該特定的胺化合物 行化學鍵結,故在含氮之芳香族 可有效地使聚醯亞胺分子內、分· 藉由上述,本發明之由液晶 向膜,可考慮係藉由直流電壓所 用變得快速,且即使於高溫下長 特性。 < (A)成分/特定聚醯亞胺> 於本發明中,(A)成分之 分子內具有羧基之聚醯亞胺即可 制。該聚醯亞胺就以四羧酸二酐 應。另外,視製作液晶配 與特定聚醯亞胺中之羧基 、形成醯胺鍵。結果,本 機溶劑中混合的簡單方法 向膜中,特定胺化合物與 之芳香族雜環,由於藉由 之功能,故可促進液晶配 液晶配向膜時,藉由含氮 之羧基形成鹽或稱爲氫鍵 在特定的聚醯亞胺中之羧 香族雜環間引起電荷移動 由於與特定的聚醯亞胺進 雜環部位上移動的電荷, 子間移動。 配向處理劑所得的液晶配 囤積的殘留電荷之緩和作 時間暴露後,仍可維持該 特定聚醯亞胺,只要是在 ’其構造上沒有特別的限 與二胺爲原料較容易取得 -13- 200831611 之理由,以使由下述式〔1〕所示重複單位之構造式所成 的聚胺基酸予以醯亞胺化的聚合物較佳。 〔化5〕(wherein 'X! is an aliphatic hydrocarbon group or a non-valent organic group, and χ2 is a nitrogen-containing aromatic heterocyclic ring) (5) as in any one of (1) to (4)' The component B) is represented by the following formula [4]: h2n (wherein X3 is an aliphatic or hydrocarbon group having a carbon number of 1 to 1 ,, and X4 is a single bond, -〇-, -NH-, - S-, a divalent organic group, and a carbon 1 of an anthracene 3 and an anthracene 4; an amine compound represented by a liquid crystal alignment treatment of an aromatic cyclic hydrocarbon group, [4] : a basal, non-aromatic ring type; 2 - or a carbon number of 1 to 19 (the total amount of the sub-components is 1 to -9-200831611 20, and X5 is a nitrogen-containing aromatic heterocyclic ring which may have a substituent). (6) Liquid crystal alignment as described in (5) The treatment agent, wherein the component (B) is an amine compound selected from the group consisting of X3, X4 and X5 of the formula [4], each selected from the group or ring combination described below, wherein the X3 system is one selected from the group consisting of carbon number 1. a straight or branched alkyl group having 1 to 10 Å, an unsaturated alkyl group having 1 to 1 carbon number, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, or a cyclooctane Alkane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, ring twelve Ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclopentadecane ring, cyclohexadecane ring, a group consisting of a tricyclohexadecane ring, a tricyclotetracosane ring, a bicyclo Gentane ring, a decahydronaphthalene ring, a raw spinane ring, and an adamantane ring; the X4 system is one selected from the group consisting of a single bond, -〇-, -NH-, -S-, -S02-, SX, -CO-0-, -〇-CO-, -CO-NH-, -NH-CO-, -CO with carbon numbers 1 to 19 -, -CF2-, -C (CF3) 2-, -CH(OH)-, -C(CH3)2-, -Si(CH3)2-, -Ο-Si(CH3)2-, -Si ( CH3) 2-〇-, -Ο-Si(CH3) 2-0-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, ring 壬An alkane ring, a cyclodecane ring, a cycloundecyl ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, Cyclooctadecane ring, cyclohexadecane ring, cycloecosane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane ring, decahydronaphthalene ring, raw spinel ring, diamond Alkane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, ring ring, ring Anthracycline, anthracene ring, phenanthrene ring, phenanene ring, pyrrole ring, oxime ring, oxime ring, thia π ring, b υ 2008 200831611 ring, pyridine ring, pyrimidine ring, quinoline ring, Pyrazoline ring, azole ring, anthracene ring, thiadiazole ring, pyridazine ring, triazine ring triazole ring, pyrazine ring, benzimidazole ring, m-diazepine phenanthroline ring, anthracene ring, a group of quinoxaline ring, benzothiazole ring oxadiazole ring, acridine ring, oxazole ring, piperazine ring, piperidine and morpholine ring, or a combination of several combinations; X5 is one type Selected from pyrrole ring, imidazole ring, spiro π ring, ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, azole ring, anthracene ring, thiadiazole ring, pyridazine ring, pyrazoline pyrazole Alkane ring, triazole ring, pyrazine ring, benzimidazole ring, Emperor I& Lin 哀, non-circular ring, 卩 卩 ring, quinoxaline D ring, phenothiazine ring, oxadiazole ring, Acridine rings, and groups of such substituents. (7) The agent according to any one of (1) to (6), which is contained in a ratio of 0. 01 to 2 moles per 1 mole of the poly(imine) component (A). (B) The agent according to any one of (1) to (7) wherein the poly(imine) of the (Α) component is heated and mixed or mixed in an organic solvent. (9) A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of the above. (10) A liquid crystal display element characterized by a liquid crystal alignment film. Isoquinoline ring, anthracene, pyrazolidine ring, tinoline ring, phenothiazine ring, ring, dioxin ring thiazole ring, pyrazole isoquinoline ring, anthracene ring, triazine ring, two The nitrogen oxime ring, the benzothiazole ring, and any one may have a carboxyl group contained in the liquid crystal alignment treatment. Liquid crystal alignment treatment Amine compound is obtained by heating (1) to (8) I is as shown in (9) -11 - 200831611 [Effect of the invention] The liquid crystal alignment treatment agent of the present invention can be obtained by a relatively simple method. Further, the liquid crystal alignment treatment agent of the present invention has a high voltage holding ratio and can obtain a liquid crystal alignment film which is rapidly neutralized by a residual charge accumulated by a direct current voltage after being exposed for a long time at a high temperature. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like. [Best Mode for Carrying Out the Invention] The liquid crystal alignment treatment agent of the present invention contains (A) a component: a polyimine having a carboxyl group in a molecule (hereinafter also referred to as a specific polyimine), and (B) a component: an amine compound having one primary amino group (-NH2) and a nitrogen-containing aromatic heterocyclic ring in a molecule, and the primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group (hereinafter also referred to as A liquid crystal alignment treatment agent which is a specific amine compound). More specifically, it is a liquid crystal alignment treatment agent obtained by mixing a specific polyimine of the component (A) and a specific amine compound of the component (B) in an organic solvent. In the present specification, the above-mentioned amine group (-NH2) is synonymous with a first-order amine group, and is hereinafter also referred to as a first-order amine group. In the liquid crystal alignment treatment agent of the present invention, it is considered that a first-stage amine group in a specific amine compound forms a salt with a carboxyl group in a specific polyimine, or a carboxyl group or a carboxyl group in a specific polyimine. With the detachment of water or alcohol, the indoleamine bond, or the ruthenium imine group in a specific polyimine, with -12-200831611 when the ring of the quinone imine group is opened and the reverse film is bonded Depending on the firing process, it is conceivable to form a first-order amine group of the salt, and the water is removed from the liquid crystal alignment treatment agent of the invention, and regardless of the presence, it is possible to effectively bond the liquid crystal with the specific polyimine. The reason. Further, the specific amine compound contains nitrogen and its conjugated structure has a charge shift in the electron-beating lateral film. Further, when the aromatic heterocyclic ring is bonded to the electrostatic interaction of the knot in the specific polyimine, the group acts on the nitrogen-containing aromatic group in the specific amine compound. In addition, the specific amine compound is chemically bonded, so that the nitrogen-containing aromatic can effectively make the polyimine molecule intramolecularly and minutely. According to the above, the liquid crystal to the film of the present invention can be considered to be DC voltage. It is used quickly and has long properties even at high temperatures. <(A) Component/Specific Polyimine] In the present invention, a polyimine having a carboxyl group in the molecule of the component (A) can be produced. The polyimine is treated with tetracarboxylic dianhydride. Further, the liquid crystal is prepared by mixing a carboxyl group in a specific polyimine to form a guanamine bond. As a result, a simple method of mixing in the solvent of the organic solvent, the specific amine compound and the aromatic heterocyclic ring, by virtue of the function, can promote the formation of a salt or a salt by a carboxyl group containing nitrogen when the liquid crystal is aligned with the liquid crystal alignment film. Hydrogen bonding causes a charge shift between the caro-aromatic heterocycles in a particular polyimine, due to the charge that moves with the particular polyamidene into the heterocyclic moiety, and moves between the sub-substituents. The relaxation of the residual charge of the liquid crystal distribution accumulated by the alignment treatment agent can maintain the specific polyimine after time exposure, as long as it is not particularly limited in its structure and the diamine is relatively easy to obtain -13- For the reason of 200831611, a polymer obtained by imidating a polyamino acid formed by a structural formula of a repeating unit represented by the following formula [1] is preferred. 〔化5〕
正整數)。 而且’式〔1〕中Ri及R2可爲同一種類,亦可爲具 有各不同種類之Ri及R2,且可組合數種不同種類作爲重 複單位。 特定的聚醯亞胺通常可藉由使上述聚胺基酸進行醯亞 胺化時之醯亞胺化率控制於未達1 0 0%予以製得。 另外’特定的聚醯亞胺可藉由在以式〔1〕所示重複 單位之構造式中使在重複單位中含有以下述式〔2〕所示 構造單位之聚胺基酸予以醯亞胺化製得。 〔化6〕Positive integer). Further, in the formula [1], Ri and R2 may be of the same type, or may have different types of Ri and R2, and a plurality of different types may be combined as a repeating unit. The specific polyimine is usually produced by controlling the imidization ratio of the above polyamino acid to less than 100% when the imidization is carried out. Further, the specific polyimine can be obtained by subjecting a polyamino acid having a structural unit represented by the following formula [2] to a repeating unit in a structural formula of a repeating unit represented by the formula [1]. Made. [6]
(式中’ R3係爲4價有機基,r4係爲2價有機基,r3或 r4中至少一個具有羧基)。 -14- 200831611 此時,醯亞胺化率亦可爲100%。 特定聚醯亞胺之醯亞胺化率,就可得高的電壓保持率 爲理由,以20%以上較佳,以40%以上更佳。 特定聚醯亞胺中羧基之量(對作爲聚醯亞胺之構造式 的重複單位而言的平均値),就可更有效地得到本發明之 效果爲理由,對作爲聚醯亞胺之構造式的重複單位而言平 均値以0.1〜3個較佳,更佳者爲〇·3〜2.0個,最佳者爲 φ 〇 · 5〜1 · 8個。此時之重複單位亦可爲組合沒有被醯亞胺化 的胺基酸基之單位者。例如,爲使由以式〔1〕所示重複 單位所成的聚醯胺酸予以醯亞胺化所得的聚醯亞胺時,醯 亞胺化率未達100%時,可考慮爲下述式〔5a〕〜〔5d〕 之構造組合所構成’以上述求得的竣基之量時的重複單位 包含全部的式〔5a〕〜〔5d〕。(wherein R3 is a tetravalent organic group, r4 is a divalent organic group, and at least one of r3 or r4 has a carboxyl group). -14- 200831611 At this time, the sulfhydrylation rate can also be 100%. The imidization ratio of the specific polyimine is preferably 20% or more, more preferably 40% or more, on the basis of a high voltage holding ratio. The amount of the carboxyl group in the specific polyimine (the average enthalpy in the repeating unit of the structural formula of the polyimine) is more effective in obtaining the effect of the present invention, and the structure as the polyimine The average repeating unit is preferably 0.1 to 3, more preferably 3 to 2.0, and the most preferred is φ 5 5 to 1 · 8. The repeating unit at this time may also be a unit combining an amino acid group which is not imidized by hydrazine. For example, in the case of a polyimine obtained by imidating a polyamic acid formed by a repeating unit represented by the formula [1], when the ruthenium imidization ratio is less than 100%, the following may be considered. The structural unit of the formula [5a] to [5d] constitutes a repeating unit of the amount of the thiol group obtained as described above, and includes all of the formulas [5a] to [5d].
於本發明中,特定聚醯亞胺中之羧基量(亦稱爲羧基 與(Η )之Q的和予以 之平均値),係以下述(i )之p、 -15- 200831611 求得。 (i)對來自沒有被醯亞胺化的胺基酸之羧基、作爲聚醯 亞胺之構造式的重複單位而言平均値:p (ii )對上述式〔2〕之R3、R4中所含的羧基、作爲聚醯 亞胺之構造式的重複單位而言平均値:Qo 其次,上述(i)中之P’可使用醯亞胺化率(z), 由下述(式1)求取。而且,醯亞胺化率(z)例如可由下 述之 <醯亞胺化率之測定 >求取。 P=2X (l-z/100) (式 1) 另外,上述(ii)之Q係爲對上述式〔2〕之R3中所 含的羧基、作爲聚醯亞胺之構造式的重複單位而言之平均 値Q!、與R4中所含的羧基、作爲聚醯亞胺之構造式的重 複單位而言之平均値Q2之和求得。 上述R3、R4各爲製得特定聚醯亞胺時所使用原料的 部分或全部之四羧酸二酐殘基(R3 )、二胺殘基(R4 )。In the present invention, the amount of the carboxyl group in the specific polyimine (also referred to as the average enthalpy of the sum of the carboxyl group and the Q of (Η)) is obtained by the following (i) p, -15-200831611. (i) For the repeating unit derived from the carboxyl group of the amino acid which is not imidized, and the structural formula of the polyimine, the average 値: p (ii ) is in the R3 and R4 of the above formula [2]. The average carboxyl group of the carboxyl group and the repeating unit of the structural formula of polyimine: Qo. Next, the P′ of (i) above can be used for the imidization ratio (z), and the following formula (1) can be used. take. Further, the ruthenium amination ratio (z) can be obtained, for example, from the measurement of <醯imination rate > P=2X (lz/100) (Formula 1) The Q of the above (ii) is a repeating unit of a structural formula represented by R3 in the above formula [2] and a structural formula of polyimine. The sum of the average 値Q!, the carboxyl group contained in R4, and the average 値Q2 as a repeating unit of the structural formula of the polyimine. Each of R3 and R4 described above is a part or all of a tetracarboxylic dianhydride residue (R3) and a diamine residue (R4) which are used as a raw material for producing a specific polyimine.
因此,上述(^係使用爲製得特定聚醯亞胺時所使用 的四羧酸二酐之合計莫耳量中下述式〔V 1〕所示四羧酸二 酐的莫耳分率,由下述式(3)求取。 〔化8〕 Ο 0Therefore, the above is the molar fraction of the tetracarboxylic dianhydride represented by the following formula [V 1] in the total molar amount of the tetracarboxylic dianhydride used in the production of the specific polyimine. It is obtained by the following formula (3). [Chemical 8] Ο 0
- 16- 200831611 Q = j3 XW /W (式3) 1112 其中,β:係表示R3中所含的羧基的個數,Wi係爲式 〔VI〕之四羧酸二酐的莫耳量,w2係表示四羧酸二酐之 合計莫耳量。 另外,上述Q2係使用爲製得特定聚醯亞胺時所使用 的二胺之合計莫耳量中以下述式〔V2〕所示之二胺的莫耳 分率,由下述式(4)求取。 〔化9〕 h2n—R4—nh2 [V2] Q=02XW/W4 试 4) 其中,β2係表示R4中所含的羧基的個數,W3係爲式 〔V2〕之二胺的莫耳量,W4係表示二胺之合計莫耳量。 如此羧基之量以下述(式5 )求取。 特定醯亞胺中之羧基的量 =P + Q1 + Q2=2X(1-Z/100) + \XW/W2W2XW/W4(式 5) 於本發明中,特定聚醯亞胺中之羧基量的調整,可以 爲(1 )藉由控制醯亞胺化率予以調整的方法、(2 )藉由 式〔2〕之R3或R4中所含的羧基數、以及式〔1〕中所示 ®複單位的構造式中式〔2〕之比例予以調整的方法中任 何一種。另外,亦可倂用(1.)與(2 )之方法。 就式〔1〕中Ri及R2之選擇自由度而言,以(1 )之 方法較佳。就特定聚醯亞胺之醯亞胺化率的選擇自由度而 言’以(2 )之方法較佳。而且,就藉由製作液晶配向膜 -17- 200831611 時之燒成製程予以醯亞胺化反應,使特定胺化合物脫離或 使聚醯亞胺鏈被切斷的可能性變少而言,以(2 )之方法 較佳。 藉由上述(1)之方法以調整特定聚醯亞胺中羧基之 量時,式〔1〕之I及h沒有特別的限制。而且,Rl及 R2於式〔1〕中可爲同種類,亦可爲具有各不同種類之 R1及R2 ’且可組合數種不同種類作爲重複單位。- 16- 200831611 Q = j3 XW /W (Formula 3) 1112 wherein β: represents the number of carboxyl groups contained in R3, and Wi is the molar amount of tetracarboxylic dianhydride of formula [VI], w2 It represents the total molar amount of tetracarboxylic dianhydride. In addition, in the above-mentioned Q2, the molar fraction of the diamine represented by the following formula [V2] in the total molar amount of the diamine used in the production of the specific polyimine is used, and the following formula (4) Seek. [9] h2n-R4-nh2 [V2] Q=02XW/W4 Test 4) wherein β2 represents the number of carboxyl groups contained in R4, and W3 is the molar amount of the diamine of formula [V2]. W4 represents the total molar amount of diamine. The amount of such a carboxyl group is determined by the following (Formula 5). The amount of the carboxyl group in the specific quinone imine = P + Q1 + Q2 = 2X (1 - Z / 100) + \XW / W2W2XW / W4 (Formula 5) In the present invention, the amount of the carboxyl group in the specific polyimine The adjustment may be (1) a method of adjusting the yield of ruthenium iodide, (2) a number of carboxyl groups contained in R3 or R4 of the formula [2], and a complex of the formula shown in the formula [1] Any one of the methods for adjusting the ratio of the formula [2] of the unit. In addition, the methods of (1.) and (2) can also be used. With respect to the degree of freedom in selecting Ri and R2 in the formula [1], the method of (1) is preferred. The method of (2) is preferred in terms of the degree of freedom of choice of the imidization ratio of the specific polyimine. Further, in the firing process in the production of the liquid crystal alignment film -17-200831611, the oxime imidization reaction is carried out to remove the specific amine compound or to reduce the possibility that the polyimine chain is cleaved. 2) The method is preferred. When the amount of the carboxyl group in the specific polyimine is adjusted by the method of the above (1), I and h of the formula [1] are not particularly limited. Further, R1 and R2 may be the same type in the formula [1], or may have different types of R1 and R2' and may be combined into several different types as repeating units.
式〔〇中之Rl具體例’如下所述。The specific example of R1 in the formula is as follows.
— 18、 200831611 〔化 1 〇〕 A-1 Α·2 h3c 、 ch3. A-3 h3c ch3 Α·4 h3c ch3 _____ 〆----- H3C CH3 A-5 女 A-6 A-7 介 A*8 XX A*9 XX A· 10 xc Α·11 ax A-12 ym A· 13 A-14 〆 ^ A· 15 A-16 A-17 A· 18 ch3 A· 19 Α·20 :h3 A.21 V ch3 A*22 A-23 x>c A-24 XX: A.25 TC Α·26 XC A-27 xa A-28 S A*29 A-30 -19- 200831611 〔化 11〕 Α·31 A-32 A-33 »xc Α-34 Xr°^CC A-35 A-36 xbrS〇c Α-37 A.38 FsC^CFa :0¾ Α·39 Α·40 ooc Α·41 OK. A-42 >m: Α·43 Α·44 CH3 ^OtC H3C A-45 CH3 h3c Α-46 ic 於此等之中,A-6、 A-16、 A-18〜A-22、 A-25、 A-37 、A-3 8及A_46,爲醯亞胺化率高的聚醯亞胺,由於對有 機溶劑之溶解性高,故較佳。 此外,1^之10莫耳%以上爲如A-1〜A-25及A-46之 具有脂環式構造或脂肪族構造時,由於可提高電壓保持率 ’故較佳。特別是I爲倂用2種選自A-1、A-16及A-19 者’由於可製得電荷之緩和作用較爲快速的液晶配向膜, 故較佳。 式〔1〕中尺2之具體例,如下所述。 -20- 200831611 〔化 1 2〕— 18, 200831611 〔化1 〇〕 A-1 Α·2 h3c, ch3. A-3 h3c ch3 Α·4 h3c ch3 _____ 〆----- H3C CH3 A-5 Female A-6 A-7 Introduction A *8 XX A*9 XX A· 10 xc Α·11 ax A-12 ym A· 13 A-14 〆^ A· 15 A-16 A-17 A· 18 ch3 A· 19 Α·20 :h3 A. 21 V ch3 A*22 A-23 x>c A-24 XX: A.25 TC Α·26 XC A-27 xa A-28 SA*29 A-30 -19- 200831611 〔化11〕 Α·31 A -32 A-33 »xc Α-34 Xr°^CC A-35 A-36 xbrS〇c Α-37 A.38 FsC^CFa :03⁄4 Α·39 Α·40 ooc Α·41 OK. A-42 > ;m: Α·43 Α·44 CH3 ^OtC H3C A-45 CH3 h3c Α-46 ic Among these, A-6, A-16, A-18~A-22, A-25, A- 37, A-3 8 and A_46, which are polyimines having a high yield of hydrazine, are preferred because of their high solubility in organic solvents. Further, when 10% or more of 1% or more of the above has an alicyclic structure or an aliphatic structure such as A-1 to A-25 and A-46, it is preferable because the voltage holding ratio can be increased. In particular, I is preferably a liquid crystal alignment film which is selected from the group consisting of two kinds of A-1, A-16 and A-19 because it can produce a rapid relaxation of charge. A specific example of the rule 2 in the formula [1] is as follows. -20- 200831611 〔化1 2〕
B-l B-2 XX B-3 xra Β·4 XJ ΙΑ B-5 H3〇xraCH3 B*6 Β*7 B-8 众 B-9 XT Β-10 〇-ch3 -ό- B-ll XCCH3 Β·12 h3c )-ch3 -0- Β-13 ch3 XX^CH3 B-14 XiC B-15 cr Β-16 B-17 B-18 Β.19 B-20 B-21 xr Β-22 B-23 ~8- B-24 8= Β-25 B-26 H3c ch3 ^0τ Β·27 ch3 h3c Β·28 PF3 ~^Sr^r F3C厂 B-29 xra B-30 xra Β·31 XrsXX B-32 B-33 -21 - 200831611 〔化 1 3〕Bl B-2 XX B-3 xra Β·4 XJ ΙΑ B-5 H3〇xraCH3 B*6 Β*7 B-8 众B-9 XT Β-10 〇-ch3 -ό- B-ll XCCH3 Β·12 H3c )-ch3 -0- Β-13 ch3 XX^CH3 B-14 XiC B-15 cr Β-16 B-17 B-18 Β.19 B-20 B-21 xr Β-22 B-23 ~8- B-24 8= Β-25 B-26 H3c ch3 ^0τ Β·27 ch3 h3c Β·28 PF3 ~^Sr^r F3C Factory B-29 xra B-30 xra Β·31 XrsXX B-32 B-33 - 21 - 200831611 〔化1 3〕
B-34 oV B-35 B-36 O^r Β·37 h3c ch3 /0¾ Β·38 f3c cf3 ira B-39 F3c cf3 Β-40 Η B*41 Β·42 Β-43 B-44 B-45 Β-46 ~QrJF^r Β·47 B.48 -Qr^Or Β·49 B-50 Β·51 iX -22 - 200831611 〔化 1 4〕B-34 oV B-35 B-36 O^r Β·37 h3c ch3 /03⁄4 Β·38 f3c cf3 ira B-39 F3c cf3 Β-40 Η B*41 Β·42 Β-43 B-44 B-45 Β-46 ~QrJF^r Β·47 B.48 -Qr^Or Β·49 B-50 Β·51 iX -22 - 200831611 〔化1 4〕
Β·52 B-53 Β-54 Μ B*55 J〇r°xi〇xr Φο 0 Β-56 iTY〇Nir^ fY B-57 U lA Β-58 wxr B*59 Β60 F B-61 h3c ch3 J7。人。XX Β·62 ch3 OgO^xr B-63 xx〇x?a〇xr Β·64 xijyb<xr B-65 众—χχα Β·66 -(CH2)n- n = 2〜12 B-67 ch3 —(CH^-C-iCH^ ch3 Β-68 ch3 一 (ch2)4-?-(ch2)3-ch3 Β·69 ch3 ch3 一 CH2_6-(CH2)2-6 - (CH2)2— Η H Β·70 ! ch3 ch3 一 CH?- G—(CH2)2· C_ (CH^— Η H B-71 ch3 ~(CH2)2-C-(CH2)5-H -23- 200831611 〔化 1 5〕Β·52 B-53 Β-54 Μ B*55 J〇r°xi〇xr Φο 0 Β-56 iTY〇Nir^ fY B-57 U lA Β-58 wxr B*59 Β60 F B-61 h3c ch3 J7 . people. XX Β·62 ch3 OgO^xr B-63 xx〇x?a〇xr Β·64 xijyb<xr B-65 众—χχα Β·66 -(CH2)n- n = 2~12 B-67 ch3 —( CH^-C-iCH^ ch3 Β-68 ch3 a (ch2)4-?-(ch2)3-ch3 Β·69 ch3 ch3 a CH2_6-(CH2)2-6 - (CH2)2— Η H Β· 70 ! ch3 ch3 - CH?- G-(CH2)2· C_ (CH^- Η H B-71 ch3 ~(CH2)2-C-(CH2)5-H -23- 200831611 [Chemical 1 5]
Β·72 ch3 —(CH^-C—(叫一 Η B-73 —(CH2)3-0-(CH2)2-0-(CH2)3- Β-74 ch3 ch3 一Si一0一Si—(ΟΗ^— ch3 ch3 B-75 -H0-(CH2)n-^Q- n = 3〜12 Β-76 XrwXX n = 2〜12 B-77 Ol0jCtwXX·^ n = 2〜12 Β*78 η = 2〜12 B-79 η = 2〜12 Β-80 XT 。一 (CH2)nCH3 η = 5〜19 B-81 XC - (CH2)nCH3 η = 5〜19 Β·82 η = 0〜21 B-83 η = 0 〜21 Β-84 η = 0〜21 B-85 η = 0〜21 Β·86 η = 0〜21 B-87 ~{ ^(CH2)nCH3 η = 0〜21 Β·88 n ±r 〇 〜21 B-89 ^^~{ y^Q(CH2)nCH3 η = 2〜19 Β·90 η = 0〜21 B-91 ^~^^~0(CH2)nCH3 η = 0 〜21 Β*92 B-93 -24 - 200831611 〔化 1 6〕Β·72 ch3 —(CH^-C—(called a B-73 —(CH2)3-0-(CH2)2-0-(CH2)3- Β-74 ch3 ch3 a Si-O-Si- (ΟΗ^—ch3 ch3 B-75 -H0-(CH2)n-^Q- n = 3~12 Β-76 XrwXX n = 2~12 B-77 Ol0jCtwXX·^ n = 2~12 Β*78 η = 2~12 B-79 η = 2~12 Β-80 XT. One (CH2)nCH3 η = 5~19 B-81 XC - (CH2)nCH3 η = 5~19 Β·82 η = 0~21 B- 83 η = 0 〜21 Β-84 η = 0~21 B-85 η = 0~21 Β·86 η = 0~21 B-87 ~{ ^(CH2)nCH3 η = 0~21 Β·88 n ± r 〇~21 B-89 ^^~{ y^Q(CH2)nCH3 η = 2~19 Β·90 η = 0~21 B-91 ^~^^~0(CH2)nCH3 η = 0 〜21 Β *92 B-93 -24 - 200831611 [Chem. 1 6]
- 25- 200831611 〔化 1 7〕- 25- 200831611 〔化1 7〕
(B-112 及 B-113 中,Q 係表示-(:0〇-、-〇〇:0-、-(:01^-、-NHCO-、-CH2-、-0-、-CO-、-NH-中任一種) 於此等之中,R2中部分或全部爲B-80〜B-101等時, 可提高液晶之預傾斜角。使液晶垂直配向時,較佳的r2 爲5〜1〇〇莫耳% (更佳者爲1〇〜8〇莫耳之b-80〜B-1〇1等之構造。 藉由上述(2)之方法以調整特定聚醯亞胺中之羧基 量時’ R3或R4中任一個具有羧基之構造即可,沒有特別 -26 - 200831611 的限制。而且,羧基之數以R3及R4各爲〇〜2個(惟R3 或R4中任一個至少具有1個羧基)較佳。 就聚醯亞胺之合成容易性、及原料之取得性而言,以 R4中具有羧基者較佳。具有羧基之R4例如B-102〜B-113 。此時,具有羧基之R4可使用丨種,亦可2種以上倂用 。另外,R4爲具有羧基時,R3之構造沒有特別的限制, 具體例如A-1〜A-46。 <特定聚醯亞胺之製造方法> 本發明所使用的(A )成分之特定聚醯亞胺的製造方 法,沒有特別的限制,一般而言使用使1種或數種選自四 羧酸及其衍生物所成的四羧酸成分、與1種或數種二胺化 合物所成的二胺成分進行反應,製得具有以式〔1〕所示 重複單位之構造式的聚醯胺酸,使該聚醯胺酸予以醯亞胺 化的方法。 φ 此時,所得的聚醯胺酸可藉由適當選擇原料之四羧酸 成分與二胺成分,形成單聚物(均聚物)或共聚物(共聚 合物)。 此處所指的四羧酸及其衍生物,爲四羧酸、四羧酸二 鹵化物及四羧酸二酐。其中,四羧酸二酐由於與二胺化合 物之反應性高,故較佳。 於下述中,係爲特定聚醯亞胺之製造方法的具體例。 例如,可使至少含有一種選自以式〔6〕所示之四羧 酸二酐的四羧酸成分、與至少含有一種選自以式〔7〕所 -27- 200831611 示之二胺化合物之二胺成分,在N-甲基吡咯烷酮、n,N,-二甲基乙醯胺、n,n,-二甲基甲醯胺、γ-丁內酯等之有機溶 劑中進行聚縮合反應,製得聚醯胺酸。 〔化 1 8〕 Ο 0(In B-112 and B-113, Q system means -(:0〇-, -〇〇:0-, -(:01^-, -NHCO-, -CH2-, -0-, -CO-, Any of -NH-) In the case where part or all of R2 is B-80 to B-101, the pretilt angle of the liquid crystal can be increased. When the liquid crystal is vertically aligned, the preferred r2 is 5~ 1〇〇mol% (more preferably 1〇~8〇mole b-80~B-1〇1, etc.) The method of (2) above is used to adjust the carboxyl group in a specific polyimine. When the amount of either R3 or R4 has a carboxyl group structure, there is no particular limitation of -26 - 200831611. Moreover, the number of carboxyl groups is 〇~2 for each of R3 and R4 (only one of R3 or R4 has at least In view of the ease of synthesis of the polyimine and the availability of the raw material, it is preferred that R4 has a carboxyl group, and R4 having a carboxyl group is, for example, B-102 to B-113. When R4 is a carboxyl group, the structure of R3 is not particularly limited, and specifically, for example, A-1 to A-46. [Specific polyimine] Manufacturing method > (A) component used in the present invention The method for producing the specific polyimine is not particularly limited, and generally, one or several kinds of tetracarboxylic acid components selected from tetracarboxylic acids and derivatives thereof, and one or several kinds of diamine compounds are used. The resulting diamine component is reacted to obtain a polylysine having a structural formula of a repeating unit represented by the formula [1], and the polyamic acid is subjected to hydrazylation. φ At this time, the obtained The polyamic acid can form a monomer (homopolymer) or a copolymer (copolymer) by appropriately selecting a tetracarboxylic acid component and a diamine component of the raw material. The tetracarboxylic acid and its derivative referred to herein, It is a tetracarboxylic acid, a tetracarboxylic acid dihalide, and a tetracarboxylic dianhydride. Among them, tetracarboxylic dianhydride is preferable because it has high reactivity with a diamine compound. Specific examples of the method for producing the amine. For example, at least one tetracarboxylic acid component selected from the group consisting of the tetracarboxylic dianhydride represented by the formula [6] and at least one selected from the group consisting of the formula [7] can be used. - 200831611 shows the diamine component of the diamine compound in N-methylpyrrolidone, n, N,-dimethyl Amides, n, n, - carry out polycondensation reaction of dimethylformamide, [gamma] -butyrolactone and the like of an organic solvent to prepare a polyamide acid of [18] Ο 0.
而且,式〔6〕之Ri係與式〔1〕之定義相同,且Ri 之具體例係如上述詳述的A-1〜A-46所記載。 〔化 1 9〕 —R2—NH2 [ 7 ] 而且,式〔7〕之R2係與式〔1〕之定義相同,且R2 之具體例係如上述詳述的B-1〜B-1 13所記載。 此時,反應溫度可選自-2〇°C〜150°C之任意溫度,較 佳者爲-5°C〜100°C之範圍。 構成四羧酸成分之化合物的合計莫耳數、與構成二胺 成分之二胺化合物的合計莫耳數之比’以〇·8〜1.2較佳。 該莫耳比接近1.0時,生成的聚合物之聚合度變大。 此外,爲製得以式〔1〕所示重複單位之構造式中部 分或全部重複單位具有以式〔2〕所示單位之聚醯胺酸時 ,可使用Rl中具有羧基之四羧酸二酐及/或R2中具有羧基 之二胺。 使聚胺基酸予以醯亞胺化的方法,一般有藉由加熱予 -28 - 200831611 以醯亞胺化、使用觸媒之觸媒醯亞胺化,以在較低溫下進 行醯亞胺化反應之觸媒醯亞胺化的方法,不易引起所得的 聚醯亞胺的分子量降低較佳。 觸媒醯亞胺化係可使聚胺基酸於有機溶劑中,在鹼性 觸媒與酸酐存在下予以攪拌下進行。此時之反應溫度爲-20 〜250°C,較佳者爲0〜180°C。反應溫度愈高者,醯亞胺 化愈快進行,惟過高時,會有聚醯亞胺之分子量降低的情 形。鹼性觸媒之量爲醯胺酸基之0 · 5〜3 0莫耳倍,較佳者 爲2〜20莫耳倍,酸酐之量爲醯胺酸基之1〜50莫耳倍, 較佳者爲3〜3 0莫耳倍。鹼性觸媒或酸酐之量少時,反應 無法充分進行,過多時,於反應完成後不易完全除去。此 時所使用的鹼性觸媒,例如吡啶、三乙胺、三甲胺、三丁 胺、三辛胺等,其中,由於舭啶於進行反應時具有適當的 鹼性,故較佳。此外,酸酐例如醋酸酐、偏苯三酸酐、均 苯四甲酸酐等,其中使用醋酸酐時,由於反應完成後容易 予以精製,故較佳。有機溶劑只要是可使聚醯胺酸溶解者 即可,沒有特別的限制,其具體例如N,N’-二甲基甲醯胺 、N,N’-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-甲基己內 酯、二甲基亞碾、四甲基尿素、二甲基颯、六甲基亞颯、 γ-己內酯等。藉由觸媒醯亞胺化之醯亞胺化率,可藉由調 節觸媒量與反應溫度、反應時間予以控制。 所生成的聚醯亞胺可藉由使上述反應溶液投入貧溶劑 中,回收生成的沉澱物予以製得。此時所使用的貧溶劑, 沒有特別的限制,例如甲醇、丙酮、己烷、丁基溶纖劑、 -29- 200831611 庚烷、甲基乙酮、甲基異丁酮、乙醇、甲苯、苯、水等。 投入貧溶劑中經沉殿的聚醯亞胺,可於過濾後’在常壓或 減壓下進行常溫或加熱乾燥,形成粉末。重複2〜1 〇次使 醯亞胺粉末再溶解於有機溶劑中,進行再沉澱的操作,亦 可使聚醯亞胺予以精製。以一次沉澱回收操作無法完全除 去雜質時,以進行該精製製程較佳。 本發明所使用的特定聚醯亞胺之分子量’沒有特別的 Φ 限制,就容易處理、且於膜形成時特性之安定性而言,重 量平均分子量以 2,000〜200,000較佳,以 4,000〜50,000 更佳。分子量係藉由GPC (凝膠滲透色層分析法)予以求 取。 < (B )成分/特定胺化合物> 本發明所使用的(B )成分之特定胺化合物,係爲在 分子內具有1個胺基(NH2)與含氮之芳香族雜環,且上 # 述胺基(1級胺基)鍵結於脂肪族烴基或非芳香族環式烴 基之胺化合物。 _ 該特定的胺化合物,由於在分子內所含的1級胺基僅 有1個,於調製液晶配向處理劑時或液晶配向劑之保管中 ’可避免引起聚合物析出或凝膠化的問題。 特定胺化合物中所含的1級胺基,就容易與特定聚醯 亞胺形成鹽或鍵結反應而言,必須於分子內鍵結於脂肪族 烴或不含芳香族烴之非芳香族環式烴基上。 脂肪族烴基之具體例,如直鏈狀烷基、具有支鏈構造 -30- 200831611 之烷基、具有不飽和鍵之烴基等。較佳者碳數爲1 更佳者碳數爲1〜15,最佳者碳數爲1〜10。 非芳香族環式烴基之具體例,如環丙烷環、環 、環戊烷環、環己烷環、環庚烷環、環辛烷環、環 、環癸烷環、環十一烷環、環十二烷環、環十三烷 十四烷環、環十五烷環、環十六烷環、環十七烷環 八烷環、環十九烷環、環二十烷環、三環二十烷環 二十二烷環、二環庚烷環、十氫萘環、原菠烷環、 烷環等。較佳者由碳數爲3〜20所成的環,更佳者 3〜1 5所成的環,最佳者由碳數3〜1 0所成的環之 族環式烴基。 特定胺.化合物中所含的含氮之芳香族雜環,係 至少一個選自下述式〔8a〕、式〔8b〕及式〔8c〕 之構造的芳香族環式烴,較佳者爲1個〜4個。 〔化 20〕 〜2 0, 丁烷環 壬烷環 環、環 、環十 、三環 及金剛 由碳數 非芳香 爲含有 所成群Further, the Ri of the formula [6] is the same as the definition of the formula [1], and the specific examples of Ri are as described in the above-mentioned A-1 to A-46. [Chem. 19] - R2 - NH2 [7] Further, the R2 of the formula [7] is the same as the definition of the formula [1], and the specific example of R2 is as described in the above-mentioned B-1 to B-1 13 Recorded. In this case, the reaction temperature may be selected from any of -2 ° C to 150 ° C, preferably from -5 ° C to 100 ° C. The ratio of the total number of moles of the compound constituting the tetracarboxylic acid component to the total number of moles of the diamine compound constituting the diamine component is preferably 〇8 to 1.2. When the molar ratio is close to 1.0, the degree of polymerization of the resulting polymer becomes large. Further, in the case where the partial or total repeating unit of the repeating unit of the formula [1] has a polylysine having a unit of the formula [2], a tetracarboxylic dianhydride having a carboxyl group in R1 can be used. And/or a diamine having a carboxyl group in R2. A method for the imidization of a polyamino acid is generally carried out by heating at -28 - 200831611 with ruthenium imidization, using a catalyst oxime imidization to carry out oxime imidization at a lower temperature. The method of imidization of the catalyst oxime of the reaction does not easily cause a decrease in the molecular weight of the obtained polyimine. The catalyst oxime imidization allows the polyamino acid to be carried out in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is -20 to 250 ° C, preferably 0 to 180 ° C. The higher the reaction temperature, the faster the ruthenium imidization, but if it is too high, the molecular weight of the polyimine will decrease. The amount of the alkaline catalyst is 0 · 5 to 30 moles of the valeric acid group, preferably 2 to 20 moles, and the amount of the acid anhydride is 1 to 50 moles of the prolyl group. The best is 3 to 3 0 moles. When the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently, and when it is too large, it is not easily removed completely after completion of the reaction. The basic catalyst to be used at this time is, for example, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, acridine is preferred because it has an appropriate basicity in carrying out the reaction. Further, an acid anhydride such as acetic anhydride, trimellitic anhydride, pyromellitic anhydride or the like, wherein acetic anhydride is used, is preferred because it is easily purified after completion of the reaction. The organic solvent is not particularly limited as long as it can dissolve the polylysine, and specifically, for example, N,N'-dimethylformamide, N,N'-dimethylacetamide, N-A Base-2-pyrrolidone, N-methylcaprolactone, dimethyl submilling, tetramethyl urea, dimethylhydrazine, hexamethylarylene, γ-caprolactone, and the like. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. The produced polyimine can be obtained by charging the above reaction solution into a poor solvent and recovering the resulting precipitate. The poor solvent to be used at this time is not particularly limited, and is, for example, methanol, acetone, hexane, butyl cellosolve, -29-200831611 heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water. Wait. The polyimine which has been introduced into the poor solvent through the sinking chamber can be subjected to normal temperature or heat drying under normal pressure or reduced pressure after filtration to form a powder. The polyimine is also recrystallized by repeating 2 to 1 times to re-dissolve the quinone imine powder in an organic solvent for reprecipitation. It is preferable to carry out the refining process when the impurities cannot be completely removed by a single precipitation recovery operation. The molecular weight of the specific polyimine used in the present invention is not particularly limited, and is easy to handle, and in terms of stability of properties at the time of film formation, the weight average molecular weight is preferably 2,000 to 200,000, more preferably 4,000 to 50,000. good. The molecular weight is determined by GPC (gel permeation chromatography). <(B) Component/Specific Amine Compound> The specific amine compound of the component (B) used in the present invention has one amine group (NH2) and a nitrogen-containing aromatic heterocyclic ring in the molecule, and # The amine group (the amine group 1) is bonded to an amine compound of an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. _ The specific amine compound has only one of the amine groups contained in the molecule, which can avoid the problem of polymer precipitation or gelation when preparing the liquid crystal alignment agent or during storage of the liquid crystal alignment agent. . The primary amine group contained in the specific amine compound is liable to form a salt or a bonding reaction with a specific polyamidiamine, and must be bonded to an aliphatic hydrocarbon or a non-aromatic ring containing no aromatic hydrocarbon in the molecule. On the hydrocarbon base. Specific examples of the aliphatic hydrocarbon group include a linear alkyl group, an alkyl group having a branched structure of -30 to 200831611, a hydrocarbon group having an unsaturated bond, and the like. Preferably, the carbon number is 1 and the carbon number is preferably 1 to 15, and the carbon number is preferably 1 to 10. Specific examples of the non-aromatic cyclic hydrocarbon group, such as a cyclopropane ring, a ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a ring, a cyclodecane ring, a cycloundecane ring, Cyclododecane ring, cyclotridecanetetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane cyclooctane ring, cyclopentadecane ring, cyclohexadecane ring, tricyclic ring Eicosanecyclotetracosane ring, bicycloheptane ring, decahydronaphthalene ring, raw spinane ring, alkane ring and the like. Preferably, it is a ring formed by a carbon number of 3 to 20, more preferably a ring of 3 to 15 carbon atoms, and most preferably a cyclic ring hydrocarbon group formed by a carbon number of 3 to 10 carbon atoms. The specific nitrogen-containing aromatic heterocyclic ring contained in the compound is at least one aromatic cyclic hydrocarbon selected from the structures of the following formula [8a], formula [8b] and formula [8c], preferably 1 ~ 4 pieces.化20] 〜2 0, butane ring decane ring ring, ring, ring ten, three ring and diamond just by carbon number non-aromatic
[8b] [8c] (式中,係爲碳數丨〜5之直鏈或支鏈烷基) 具體而s ’例如吡咯環、咪唑環、噁唑環、噻 吡唑環、吡啶環、嘧啶環、喹啉環、吡唑啉環、異 、昨唑環、嘌呤環、噻二唑環、噠嗪環、三嗪環、 環、二唑^、毗嗪環、苯并咪唑環、間二氮茚環、 唑環、 喹啉環 吡唑烷 蒂諾啉 -31 - 200831611 環、菲繞啉環、吲哚環、喹喔啉環、苯并噻唑環、吩噻嗪 環、噁二哩環、卩丫啶環等。另外,此等含氮之芳香族雜環 的碳原子,亦可具有含雜原子之取代基。 更佳的特定胺化合物,係爲以下述式〔3〕所示之胺 化合物。 〔化 2 1〕[8b] [8c] (wherein, it is a linear or branched alkyl group having a carbon number of 丨~5) specifically s 'such as a pyrrole ring, an imidazole ring, an oxazole ring, a thipyraz ring, a pyridine ring, a pyrimidine Ring, quinoline ring, pyrazoline ring, iso, oxazolyl ring, anthracene ring, thiadiazole ring, pyridazine ring, triazine ring, ring, diazole ^, pyrazine ring, benzimidazole ring, two Aziridine ring, azole ring, quinoline ring pyrazolidine lininoline-31 - 200831611 ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazine ring , acridine ring, etc. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring may have a substituent containing a hetero atom. More preferably, the specific amine compound is an amine compound represented by the following formula [3]. 〔化 2 1〕
[3] (式中,Xi係爲具有脂肪族烴基或非芳香族環式烴基之2 價有機基,X2係爲含氮之芳香族雜環) 於式〔3〕中,X!只要是具有脂肪族烴基或非芳香族 環式煙基之2價有機基即可,沒有特別的限制。[3] (wherein, Xi is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and X2 is a nitrogen-containing aromatic heterocyclic ring). In the formula [3], X! The divalent organic group of the aliphatic hydrocarbon group or the non-aromatic ring-type nicotyl group is not particularly limited.
式〔3〕中較佳的X!,係爲具有i種選自碳數1〜2〇 之脂肪族烴基及碳數3〜20之非芳香族環式烴基的2價有 機基。非芳香族環式烴基例如上述之構造。更佳者爲碳數 1〜1 5之脂肪族烴基,例如環丙烷環、環丁烷環、環戊烷 環、環己烷環、環庚烷環、環辛烷環、環壬烷環、環癸烷 環、環十一烷環、環十二烷環、環十三烷環、環十四烷環 、原菠烷環、金剛烷環等。更佳者爲碳數1〜1 〇之直鏈或 支鏈烷基。 此外,X!中所含的沒有鄰接於胺基之任意脂肪族烴基 或非芳香族環式烴基中之-CH2-,亦可以-〇-、-NH-、 -CO-0-、-o-co-、-CO-NH-、-NH-CO-、-CO-、-S-、 -S ( 0) 2-、-CF2-、-C ( CF3 ) 2-、-c ( CH3 ) 2-、 -32 - 200831611 -Si ( CH3 ) 2-、-Ο-Si ( CH3 ) 2-、_Si ( CH3) 2-0_、 -O · S i ( C H 3 ) 2 - 0 -、環狀烴基及雜環取代。而且,鍵結於 任意碳原子之氫原子,亦可以碳數1〜20之直鏈或支鏈烷 基、環狀烴基、碳數1〜丨〇之含氟烷基、雜環、氟原子, 羥基取代。 環狀烴基之具體例’如苯環、萘環、四氫萘環、莫環 、茚環、芴環、蒽環、菲環、菲那烯(Phenalene )環、環 φ 丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、環 辛烷環、環壬烷環、環癸烷環、環十一烷環、環十二烷環 、環十三烷環、環十四烷環、環十五烷環、環十六烷環、 環十七烷環、環十八烷環、環十九烷環、環二十烷環、三 環二十烷環、三環二十二烷環、二環庚烷環、十氫萘環、 原菠烷環、金剛烷環等。 此外,雜環之具體例如卩ϋ略環、咪π坐環、π惡嗤環、噻 唑環、吡唑環、吡啶環、嘧啶環、喹啉環、吡唑啉環、異 ® 喹啉環、咔唑環、嘌呤環、噻二唑環、噠嗪環、三嗪環、 吡唑烷環、三唑環、吡曝環、苯并咪唑環、間二氮茚環、 帝諾啉環、非繞啉環、11引哄環、喹喔啉環、苯并噻哩環、 吩噻嗪環、噁二唑環、吖啶環等。 式〔3〕中Χ2係爲含氮之芳香族雜環,與上述相同地 爲至少含有1個選自式〔8a〕、式〔8b〕及式〔8c〕所成 群之構造的芳香族環式烴。其具體例如上述之構造。於此 等之中,以毗略環、咪唑環、吡唑環、吡啶環、嘧啶環、 噠嗪埃、二嗪環、二唑環、吡嗪環、苯并咪唑環、間二氮 -33 - 200831611 茚環、喹喔啉環、吖庚因環、二吖庚因環、 環、酞曝環較佳。 而且,就含氮之芳香族雜環與特定聚醯 形成鹽或稱爲氫鍵之靜電相互作用的容易值 沒有與X2中所含的式〔8a〕、式〔8b〕、 鄰的取代基鍵結較佳。 另外,式〔3〕之X2的含氮芳香族雜環 可具有鹵素原子及/或有機基之取代基,該 有氧原子、硫原子、氮原子等之雜原子。 式〔3〕中較佳的Χι與χ2之組合,係: 選自碳數1〜20之脂肪族烴基及碳數3〜2〇 式烴基的2價有機基,Χ2係爲選自吡咯環、 環、吡D定環、嘧D定環、噠曉環、三嗪環、三 、苯并咪唑環、間二氮茚環、喹喔啉環、口、广 庚因環、萘D定環、菲嗪環、酞嗪環。而且, 族雜環的碳原子,亦可具有鹵素原子及/或 基,該有機基亦可含有氧原子、硫原子、氮 子。 更佳的特定胺化合物,係爲以下述式丨 化合物。 〔化 22〕 /Χ3 /Χ5 H2N’[4] (式中’ X3係爲碳數1〜10之脂肪族烴基、 萘啶環、菲嗪 亞胺中之羧基 i而言,以 X i 及式〔8 c〕相 的碳原子,亦 有機基亦可含 爲具有1種 之非芳香族環 咪唑環、吡唑 唑環、吡嗪環 庚因環、二吖 X2之含氮芳香 有機基之取代 原子等之雜原 :4〕所示之胺 非芳香族環式 -34- 200831611 烴基,X4係爲單鍵、-0-、-NH-、-S-、-S〇2·或碳數1〜19 之2價有機基,且χ3與χ4具有的碳原子之合計量爲1〜 2〇,Χ5係爲可具有取代基之含氮的芳香族雜環)。 式〔4〕之Χ3係爲碳數1〜1 0之脂肪族烴基、或非芳 香族環式烴基。其具體例如碳數1〜1 〇之直鏈或支鏈烷基 、碳數1〜10之不飽和烷基、環丙烷環、環丁烷環、環戊 烷環、環己烷環、環庚烷環、環辛烷環、環壬烷環、環癸 烷環、環十一烷環、環十二烷環、環十三烷環、環十四烷 環、環十五烷環、環十六烷環、環十七烷環、環十八烷環 、環十九烷環、環二十烷環、三環二十烷環、三環二十二 烷環、二環庚烷環、十氫萘環、原菠烷環、金剛烷環等。 較佳者爲碳數1〜1 0之直鏈或支鏈烷基、環丙烷環、環丁 烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環、環壬 烷環、環癸烷環、環十一烷環、環十二烷環、環十三烷環 、環十四烷環、原菠烷環、金剛烷環。更佳者爲碳數1〜 1 〇之直鏈或支鏈烷基。 χ3中所含的、沒有鄰接於胺基之任意脂肪族烴基或非 芳香族環式烴基中之-CH2-,亦可以-0-、^11-、-(:0-0-、-O-CO-、-CO-NH-、-NH-CO-、-CO-、s-、-S ( 0) 2-、 -CF2-、-C ( CF3 ) 2-、-C ( CH3) 2-、-Si ( ch3) 2-、 •0 賴 Si ( CH3) 2-、-Si ( CH3) 2-0…-Ο-Si ( CH3) 2-0-、環 狀烴基及雜環取代。而且,鍵結於任意碳原子之氫原子, 亦可以碳數1〜2 0之直鏈或支鏈烷基、環狀烴基、碳數1 〜1 0之含氟烷基、雜環、氟原子,羥基取代。此處所指的 -35- 200831611 環狀烴基及雜環,係與式〔1〕之Χι所述者同義。 式〔4〕之X4係爲單鍵、·〇-、-NH-、-S-、-S02-或礙 數1〜1 9之2價有機基。該碳數1〜1 9之2價有機基,係 爲具有1〜1 9個碳原子之2價有機基,亦可含有氧原子、 氮原子、硫原子、矽原子等。該X4之具體例如下所述。 例如單鍵、-0-、-NH-、-S -、-S02-或碳數1〜19之徑 基、-CO-O-、-0-C0-、-CO-NH-、-NH-CO-、-CO-、-cp】 、-C(CF3) 2-、-CH(OH) -、-C(CH3) 2-、 -Si ( CH3) 2-、-〇-Si ( CH3) 2-、-Si ( CH3) 2-O-、 -O - S i ( C H 3 ) 2 - 〇 -、環丙烷環、環丁烷環、環戊烷環、環 己烷環、環庚烷環、環辛烷環、環壬烷環、環癸烷環、環 十一烷環、環十二烷環、環十三烷環、環十四烷環、環十 五烷環、環十六烷環、環十七烷環、環十八烷環、環十九 院環、環二十院環、三環二十院環、三環二十二院環、二 環庚烷環、十氫萘環、原菠烷環、金剛烷環、苯環、萘環 、四氫萘環、葜環、茚環、芴環、蒽環、菲環、菲那烯( P h e n a 1 e n e )環、卩比咯環、咪Π坐環、D惡唑環、噻P坐環、啦口坐 環、吡啶環、嘧啶環、喹啉環、吡唑啉環、異喹啉環、昨 唑環、嘌呤環、噻二唑環、噠嗪環、三嗪環、吡唑烷環、 三唑環、吡嗪環、苯并咪唑環、間二氮茚環、蒂諾啉環、 菲繞啉環、吲哚環、喹喔啉環、苯并噻唑環、吩噻嗪環、 噁二唑環、吖啶環、噁唑環、哌嗪環、哌啶環、二噁烷環 及嗎啉環等。X4亦可含有2種以上此等。 含有2種以上之具體例,如-NH-CH2-、-NH-C2H4-、 -36- 200831611 NH-C3H6·、-NH-C4H8-、-S-CH2-、-S-C2H4-、-s-c3h6-、 -S-C4H8-、-O-CH2-、-O-C2H4-、-0-C3H6-、-O-CzjHg-、 -NH-CO-CH2-、-NH-CO-C2H4-、-NH-CO-C3H6-、 -NH-CO-C4H8、-CO-CH2-、-CO-C2H4-、-CO-C3H6-、 -CO-C4H8-、-CO-NH-CH2·、-co-nh-c2h4-、The preferred X! in the formula [3] is a divalent organic group having i kinds of aliphatic hydrocarbon groups selected from the group consisting of 1 to 2 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. The non-aromatic cyclic hydrocarbon group is, for example, the above configuration. More preferably, it is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a raw spinane ring, an adamantane ring, and the like. More preferably, it is a linear or branched alkyl group having a carbon number of 1 to 1 Å. Further, -CH2- contained in any of the aliphatic or non-aromatic cyclic hydrocarbon groups adjacent to the amine group contained in X! may also be -〇-, -NH-, -CO-0-, -o- Co-, -CO-NH-, -NH-CO-, -CO-, -S-, -S ( 0) 2-, -CF2-, -C ( CF3 ) 2-, -c ( CH3 ) 2- , -32 - 200831611 -Si (CH3) 2-, -Ο-Si (CH3) 2-, _Si (CH3) 2-0_, -O · S i ( CH 3 ) 2 - 0 -, cyclic hydrocarbon group and hetero Ring replacement. Further, a hydrogen atom bonded to any carbon atom may be a linear or branched alkyl group having a carbon number of 1 to 20, a cyclic hydrocarbon group, a fluorine-containing alkyl group having a carbon number of 1 to fluorene, a heterocyclic ring or a fluorine atom. Hydroxyl substitution. Specific examples of the cyclic hydrocarbon group such as a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a molybdenum ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, a phenanene ring, a ring φ propane ring, or a cyclobutane a ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, a cycloundecyl ring, a cyclododecane ring, a cyclotridecane ring, Cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclopentadecane ring, cyclohexadecane ring, tricyclohexadecane ring, three Cyclotetradecane ring, bicycloheptane ring, decahydronaphthalene ring, raw spinach ring, adamantane ring, and the like. Further, specific examples of the heterocyclic ring are, for example, a ring, a π ring, a π ox ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, Indazole ring, anthracene ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyridene ring, benzimidazole ring, m-diazepine ring, dinoline ring, non A porphyrin ring, an 11th hydrazine ring, a quinoxaline ring, a benzothiazepine ring, a phenothiazine ring, an oxadiazole ring, an acridine ring or the like. In the formula [3], the oxime 2 is a nitrogen-containing aromatic heterocyclic ring, and similarly to the above, an aromatic ring having at least one structure selected from the group consisting of the formula [8a], the formula [8b] and the formula [8c] Hydrocarbon. Specifically, for example, the configuration described above. Among these, a contiguous ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine, a diazine ring, a diazole ring, a pyrazine ring, a benzimidazole ring, and a m-diaza-33 - 200831611 Anthracycline, quinoxaline ring, azepine ring, dioxetane ring, ring, anthracene ring are preferred. Further, the easy value of the electrostatic interaction of the nitrogen-containing aromatic heterocyclic ring with a specific polyfluorene to form a salt or a hydrogen bond is not the same as the substituent of the formula [8a], the formula [8b], and the adjacent substituent contained in X2. The knot is better. Further, the nitrogen-containing aromatic heterocyclic ring of X2 of the formula [3] may have a substituent of a halogen atom and/or an organic group, and a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. The preferred combination of Χι and χ2 in the formula [3] is: a divalent organic group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 3 to 2 carbon atoms, and the oxime 2 is selected from the group consisting of pyrrole rings. Ring, pyridyl D ring, pyrimidine D ring, indole ring, triazine ring, tris, benzimidazole ring, m-diazepine ring, quinoxaline ring, mouth, Guang Geng ring, naphthalene D ring, A phenazine ring, a pyridazine ring. Further, the carbon atom of the group heterocyclic ring may have a halogen atom and/or a group, and the organic group may further contain an oxygen atom, a sulfur atom or a nitrogen atom. More preferably, the specific amine compound is a compound of the formula shown below. [Chem. 22] /Χ3 /Χ5 H2N'[4] (wherein X3 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group i in a naphthyridine ring or a phenazineimine, and X i and The carbon atom of the [8c] phase may also be substituted by a nitrogen-containing aromatic organic group having one non-aromatic cyclic imidazole ring, pyrazolazole ring, pyrazine cycloheptene ring and dioxane X2. Atoms such as atoms: 4) amine non-aromatic ring -34- 200831611 hydrocarbon group, X4 is a single bond, -0-, -NH-, -S-, -S〇2· or carbon number 1 The hexavalent organic group of ~19, and the total of the carbon atoms of χ3 and χ4 is 1 to 2〇, and the Χ5 is a nitrogen-containing aromatic heterocyclic ring which may have a substituent. The oxime 3 of the formula [4] is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a non-aromatic aromatic hydrocarbon group. Specifically, for example, a linear or branched alkyl group having 1 to 1 carbon atom, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane. Alkane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, ring ten Hexacyclo ring, cycloheptadecane ring, cyclooctadecane ring, cyclodecadecane ring, cyclohexadecane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane ring, ten Hydrogen naphthalene ring, raw spinel ring, adamantane ring, and the like. Preferred is a linear or branched alkyl group having a carbon number of 1 to 10, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, or a ring oxime. An alkane ring, a cyclodecane ring, a cycloundecyl ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a raw spinane ring, an adamantane ring. More preferably, it is a linear or branched alkyl group having a carbon number of 1 to 1 fluorene. -CH2- contained in χ3, which is not adjacent to any of the aliphatic or non-aromatic cyclic hydrocarbon groups of the amine group, may also be -0, -11-, -(:0-0-, -O- CO-, -CO-NH-, -NH-CO-, -CO-, s-, -S (0) 2-, -CF2-, -C (CF3) 2-, -C (CH3) 2-, -Si ( ch3) 2-, •0 Lai Si (CH3) 2-, -Si (CH3) 2-0...-Ο-Si (CH3) 2-0-, a cyclic hydrocarbon group and a heterocyclic ring. a hydrogen atom bonded to any carbon atom, or a linear or branched alkyl group having a carbon number of 1 to 20, a cyclic hydrocarbon group, a fluorine-containing alkyl group having a carbon number of 1 to 10, a heterocyclic ring, a fluorine atom, or a hydroxy group. The -35-200831611 cyclic hydrocarbon group and heterocyclic ring referred to herein are synonymous with those described in the formula [1]. The X4 system of the formula [4] is a single bond, 〇-, -NH-, -S -, -S02- or a divalent organic group having a hindrance of 1 to 19. The divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may also contain An oxygen atom, a nitrogen atom, a sulfur atom, a ruthenium atom, etc. The specificity of the X4 is as follows. For example, a single bond, -0-, -NH-, -S-, -S02- or a carbon number of 1 to 19 , -CO-O-, -0-C0-, -CO-NH-, -NH-CO- , -CO-, -cp], -C(CF3) 2-, -CH(OH) -, -C(CH3) 2-, -Si(CH3) 2-, -〇-Si (CH3) 2-, -Si(CH3)2-O-, -O - S i ( CH 3 ) 2 - 〇-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane Alkane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, ring Heptadecane ring, cyclooctadecane ring, ring nine yard ring, ring twenty yard ring, three ring twenty yard ring, three ring twenty-two courtyard ring, two-ring heptane ring, decahydronaphthalene ring, original Pentane ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, anthracene ring, anthracene ring, phenanthrene ring, phenanthene (P hena 1 ene ) ring, fluorene ring, Sodium ring, D-oxazole ring, Thio-P ring, s-ring ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, azole ring, anthracene ring, thiadiazole Ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, m-diazepine ring, tenoxo ring, phenanthroline ring, anthracene ring, quin a porphyrin ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring, an oxazole ring, a piperazine ring, a piperidine ring, a dioxane ring, a morpholine ring, etc. X4 may also contain two kinds. The above. There are two or more specific examples, such as -NH-CH2-, -NH-C2H4-, -36-200831611 NH-C3H6·, -NH-C4H8-, -S-CH2-, -S-C2H4 -, -s-c3h6-, -S-C4H8-, -O-CH2-, -O-C2H4-, -0-C3H6-, -O-CzjHg-, -NH-CO-CH2-, -NH-CO -C2H4-, -NH-CO-C3H6-, -NH-CO-C4H8, -CO-CH2-, -CO-C2H4-, -CO-C3H6-, -CO-C4H8-, -CO-NH-CH2· , -co-nh-c2h4-,
-CO-NH-C3H6-、-CO-NH-C4H8-、-NH-CH2-CH ( CH3) -、 -NH-C2H4-CH ( CH3) -、-NH-C3H6-CH ( CH3)-、 -NH-C4H8-CH ( CH3) -、-S-CH2-CH ( CH3)-、 -S-C2H4-CH ( ch3 ) -、-S-C3H6-CH ( CH3 )-、 -S-C4H8-CH ( CH3) -、-0-CH3-CH ( CH3)-、 -o-c2h4-ch ( CH3 ) 、-0-C3H6-CH ( CH3 )-、 -0-C4H8-CH ( CH3) -、-NH-CO-CH2-CH ( CH3)-、 -nh-co-c2h4-ch ( ch3 ) ·、-NH-CO-C3H6-CH ( ch3 )-、-NH-CO-C4H8-CH ( CH3) -、-CH ( OH) -CH2-、 -CH ( OH) -C2H4-、-CH ( OH) -C3H6-、 -CH ( OH) -C4H8-、-CH ( CH2OH) -CH2-、 -CH ( CH2OH) -C2H4-、-CH ( CH2OH) -C3H6-、 -CH ( CH2OH) -C4H8-、-NH-CH ( CH2OH ) -CH2-、 -CO-NH-CH ( CH2OH) -CH2-、 -NH-CO-CH ( CH2OH ) -CH2-、-CO-CH ( CH2〇H ) -CH2- 、-S-CH ( CH2OH ) -CH2-、-O-CH ( CH2OH ) -CH2-、 -CH ( N ( CH3) 2 ) -、-C6H4-0-、-C6H4-NH-、 -C6H4-CO-NH-、-C6H4-NH-CO-、-C6H4-CO-、-C6H4-CH2-、-C 6 η 4 - S -等。 37- 200831611 式〔4〕之Χ5係爲含氮之芳香族雜環,與式〔3〕之 Χ2相同,因此,Χ5與Χ2之定義相同。其具體例如與上述 Χ2相同的構造。於此等之中,以吡咯環、咪唑環、吡唑環 、吡D定環、嘧卩定環、噠曉環、三曉環、吡哩院環、三哩環 、吡嗪環、苯并咪嗤環、間二氮茚環、喹喔啉環、吖庚因 環、二吖庚因環、萘啶環、菲嗪環、酞嗪環較佳。 此外,就含氮之芳香族雜環與特定聚醯亞胺中之羧基 • 形成鹽或稱爲氫鍵之靜電互相作用的容易性而言,以Χ4 沒有與Χ5中所含的式〔8a〕、式〔8b〕及式〔8c〕相鄰 的碳原子鍵結較佳。 而且,式〔4〕中X5之含氮芳香族雜環的碳原子,亦 可具有鹵素原子及/或有機基之取代基,該有機基亦可含 有氧原子、硫原子、氮原子等之雜原子。 式〔4〕中較佳的X3、X4及χ5之組合,係χ3爲碳數 1〜1 0之直鏈或支鏈院基、環丙院環、環丁院環、環戊院 • 環、環己烷環、環庚烷環、環辛烷環、環壬烷環、環癸烷 環、環十一烷環、環十二烷環、環十三烷環、環十四烷環 、原菠烷環、金剛烷環,X4係爲單鍵、碳數1〜1 〇之直鏈 或支鏈烷基、-0-、-ΝΗ-、-CO-0-、-〇_c〇-、-CO-NH-、 _NH-CO_、-CO_、_S_、_S02…-CF2-、_c ( CF3) 2_、 -Si ( CH3 ) ”、_0_Si ( ch3) 2-、_Si ( ch3) 2-0- ' -〇-Si(CH3)2_〇-、-CH(OH)-、_NH-CH2-、_NH-C2H4-、-NH-C3H6-、-NH-C4H8·、,S-CH2_、-S-C2H4-、S-C3H6-> -S-C4H8- ' -O-CH2- ' -O-C2H4- - -O-C3H6- N -0-C4H8- ' -38 - 200831611 -NH-CO-CH2-、-NH-CO-C2H4·、-NH-CO-C3H6-、 -NH-CO-C4H8' ' -CO-CH2· Λ -CO-C2H4- λ -CO-C3H6- ' -CO-C4H8-、-CO-NH-CH2-、-CO-NH-C2H4-、 -CO-NH-C3H6-、-CO、NH-C4H8-、-nh-ch2-ch ( ch3)-、 -NH-C2H4-CH ( CH3) -、-NH-C3H6-CH ( CH3)-、 -NH-C4H8-CH ( CH3) -、-S-CH2-CH ( CH3)-、 -S-C2H4-CH ( CH3) - -S-C3H6-CH ( CH3)- '-CO-NH-C3H6-, -CO-NH-C4H8-, -NH-CH2-CH(CH3)-, -NH-C2H4-CH(CH3)-, -NH-C3H6-CH (CH3)-, - NH-C4H8-CH (CH3) -, -S-CH2-CH (CH3)-, -S-C2H4-CH (CH3)-, -S-C3H6-CH (CH3)-, -S-C4H8-CH ( CH3) -, -0-CH3-CH (CH3)-, -o-c2h4-ch (CH3), -0-C3H6-CH (CH3)-, -0-C4H8-CH (CH3) -, -NH- CO-CH2-CH ( CH3)-, -nh-co-c2h4-ch ( ch3 ) ·, -NH-CO-C3H6-CH ( ch3 )-, -NH-CO-C4H8-CH ( CH3) -, - CH(OH)-CH2-, -CH(OH)-C2H4-, -CH(OH)-C3H6-, -CH(OH)-C4H8-, -CH(CH2OH)-CH2-, -CH(CH2OH)- C2H4-, -CH(CH2OH)-C3H6-, -CH(CH2OH)-C4H8-, -NH-CH(CH2OH)-CH2-, -CO-NH-CH(CH2OH)-CH2-, -NH-CO- CH ( CH2OH ) -CH2-, -CO-CH ( CH2〇H ) -CH2- , -S-CH ( CH2OH ) -CH2-, -O-CH ( CH2OH ) -CH2-, -CH ( N ( CH3) 2) -, -C6H4-0-, -C6H4-NH-, -C6H4-CO-NH-, -C6H4-NH-CO-, -C6H4-CO-, -C6H4-CH2-, -C 6 η 4 - S -etc. 37-200831611 The oxime 5 of the formula [4] is a nitrogen-containing aromatic heterocyclic ring, which is the same as the oxime 2 of the formula [3], and therefore, Χ5 and Χ2 have the same definitions. Specifically, for example, it has the same configuration as that of the above Χ2. Among them, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridyl ring, a pyridinium ring, a guanidine ring, a triple ring, a pyridoxine ring, a triterpene ring, a pyrazine ring, a benzophenone The oxime ring, the m-diazepine ring, the quinoxaline ring, the azepine ring, the dioxetane ring, the naphthyridine ring, the phenazine ring, and the pyridazine ring are preferred. Further, in the case of the ease of interaction between the nitrogen-containing aromatic heterocyclic ring and the carboxyl group in the specific polyimine, which forms a salt or a hydrogen bond, the enthalpy 4 does not have the formula [8a] contained in Χ5. Preferably, the carbon atoms of the formula [8b] and the formula [8c] are bonded. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of X5 in the formula [4] may have a substituent of a halogen atom and/or an organic group, and the organic group may further contain an oxygen atom, a sulfur atom, a nitrogen atom or the like. atom. The preferred combination of X3, X4 and χ5 in the formula [4] is that the χ3 is a linear or branched chain base having a carbon number of 1 to 10, a ring of a propylene ring, a ring of a ring, a ring of a ring, and a ring. Cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclodecane ring, cyclodecane ring, cycloundecyl ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, original a spinane ring, an adamantane ring, a linear or branched alkyl group having a single bond, a carbon number of 1 to 1 、, -0-, -ΝΗ-, -CO-0-, -〇_c〇-, -CO-NH-, _NH-CO_, -CO_, _S_, _S02...-CF2-, _c (CF3) 2_, -Si (CH3) ”,_0_Si (ch3) 2-, _Si (ch3) 2-0- ' -〇-Si(CH3)2_〇-, -CH(OH)-, _NH-CH2-, _NH-C2H4-, -NH-C3H6-, -NH-C4H8·, S-CH2_, -S-C2H4 -, S-C3H6-> -S-C4H8- '-O-CH2- ' -O-C2H4- - -O-C3H6- N -0-C4H8- ' -38 - 200831611 -NH-CO-CH2-, -NH-CO-C2H4·, -NH-CO-C3H6-, -NH-CO-C4H8' '-CO-CH2· Λ -CO-C2H4- λ -CO-C3H6- ' -CO-C4H8-, -CO -NH-CH2-, -CO-NH-C2H4-, -CO-NH-C3H6-, -CO, NH-C4H8-, -nh-ch2-ch (ch3)-, -NH-C2H4-CH (CH3) -, -NH-C3H6-CH (CH3)-, -NH-C4H8-CH (CH3) -, -S-CH2-CH (CH3)-, -S-C2H4-CH (CH3) - -S-C3H6-CH (CH3)- '
-S-C4H8-CH ( CH3) -、-0-CH3-CH ( CH3)-、 -O-C2H4-CH ( ch3 ) -、-0-C3H6-CH ( CH3 )-、 -0-C4H8-CH ( CH3) -、-NH-CO-CH2-CH ( CH3)-、 -nh-co-c2h4-ch ( CHs ) -、-NH-CO-C3H6-CH ( CH3 )-、-NH-CO-C4H8-CH ( CH3) -、-CH ( OH) -CH2-、 -CH ( OH) -C2H4-、-CH ( OH) -C3H6-、 CH ( OH) -C4H8-、-CH ( CH2OH) -CH2-、 -CH ( CH2OH) -C2H4-、-CH ( CH2OH) -C3H6-、 -CH ( CH2OH) -C4H8-、-NH-CH ( CH2OH) _CH2-、 -CO-NH-CH ( CH2OH) -CH2-、 -NH-CO-CH ( CH2OH) -CH2-、 -CO-CH ( CH2〇H ) -CH2-、-S-CH ( CH2OH ) -CH2-、 -O-CH ( CH2OH ) -CH2-、-CH ( N ( CH3) 2 ) -、-C6H4 〇 、-C6H4-NH-、-C6H4-CO-NH-、-C6H4-NH-CO-、 -C6H4-CO-、-C6H4-CH2-、-C6H4-S-、環丙垸環、環丁 严严 、環戊烷環、環己烷環、環庚烷環 '環辛烷環、環壬院環 、環癸烷環、環十一烷環、環十二烷環、原菠烷環、金剛 -39- 200831611 烷環、苯環、萘環、四氫萘環、奠環、茚環、芴環、蒽環 、菲環、菲那烯(Phenalene )環,Χ5爲吡咯環、咪唑環 、吡卩坐環、吡卩定環、嘧D定環、噠曉環、三嗪環、三哇環、 吡嗪環、苯并咪唑環、間二氮茚環、喹喔啉環、吖庚因環 、二吖庚因環、萘啶環、菲嗪環、酞嗪環。此外,Χ5之含 氮芳香族雜環的碳原子,亦可具有鹵素原子及/或有機基 ,該有機基亦可含有氧原子、硫原子、氮原子等之雜原子 〇 較佳的式〔4〕中Χ3、Χ4及之組合,係Χ3爲選自 碳數1〜5直鍵或支鍵院基、環丙院ϊ哀、Ϊ5 丁院環、環戊 烷環、環己烷環、環庚烷環、原菠烷環、金剛烷環,Χ4爲 選自單鍵、碳數1〜5之直鏈或支鏈烷基、-0-、->^-、-CO-O-、-O-CO-、-CO-NH-、-NH-CO-、-CO-、-S-、 -s(o)2-、-ch(oh)-、-nh-ch2-、-s-ch2-、-o-ch2-、-o-c2h4-、-nh-co-ch2-、-co-ch2-、-co-nh-ch2-、-S-C4H8-CH ( CH3) -, -0-CH3-CH ( CH3)-, -O-C2H4-CH ( ch3 ) -, -0-C3H6-CH ( CH3 )-, -0-C4H8-CH (CH3) -, -NH-CO-CH2-CH (CH3)-, -nh-co-c2h4-ch (CHs) -, -NH-CO-C3H6-CH (CH3)-, -NH-CO-C4H8 -CH(CH3)-, -CH(OH)-CH2-, -CH(OH)-C2H4-, -CH(OH)-C3H6-, CH(OH)-C4H8-, -CH(CH2OH)-CH2- , -CH ( CH2OH) -C2H4-, -CH ( CH2OH) -C3H6-, -CH ( CH2OH) -C4H8-, -NH-CH ( CH2OH) _CH2-, -CO-NH-CH ( CH2OH) -CH2- -NH-CO-CH(CH2OH)-CH2-, -CO-CH(CH2〇H)-CH2-, -S-CH(CH2OH)-CH2-, -O-CH(CH2OH)-CH2-,- CH ( N ( CH3) 2 ) -, -C6H4 〇, -C6H4-NH-, -C6H4-CO-NH-, -C6H4-NH-CO-, -C6H4-CO-, -C6H4-CH2-, -C6H4 -S-, cyclopropane ring, cyclobutyl, cyclopentane ring, cyclohexane ring, cycloheptane ring 'cyclooctane ring, ring 壬 ring, cyclodecane ring, cycloundecyl ring, Cyclododecane ring, raw spinel ring, diamond-39-200831611 alkane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, ring ring, anthracene ring, anthracene ring, anthracene ring, phenanthrene ring, phenanene (Phenalene) Ring, Χ5 is pyrrole ring, imidazole ring, pyridyl Ring, pyridazine ring, pyrimidine D ring, oxime ring, triazine ring, triwax ring, pyrazine ring, benzimidazole ring, m-diazepine ring, quinoxaline ring, azepine ring, Dioxane ring, naphthyridine ring, phenazine ring, pyridazine ring. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Χ5 may have a halogen atom and/or an organic group, and the organic group may also contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. 〕中Χ3,Χ4 and combinations thereof, the system Χ3 is selected from the group consisting of carbon number 1~5 direct bond or branch bond base, ring propyl sorrow, Ϊ5 dingyuan ring, cyclopentane ring, cyclohexane ring, cycloglycan An alkane ring, a raw porphyrin ring, an adamantane ring, Χ4 is a linear or branched alkyl group selected from a single bond, having a carbon number of 1 to 5, -0-, ->^-, -CO-O-, - O-CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -s(o)2-, -ch(oh)-, -nh-ch2-, -s-ch2 -, -o-ch2-, -o-c2h4-, -nh-co-ch2-, -co-ch2-, -co-nh-ch2-,
-NH-CH2-CH ( CH3) -、-S-CH2-CH ( CH3)-、 -0-CH3-CH ( CH3) -、-NH-CO-CH2-CH ( CH3)-、 -CH ( OH) -CH2-、-CH ( OH) -C2H4-、 -CH ( CH2OH) -CH2-、-NH-CH ( CH2OH) -CH2-、 -CO-NH-CH ( CH2OH) -CH2-、 -NH-CO-CH ( CH2OH ) -CH2-、-CO-CH ( CH2〇H ) -CH2- 、-S-CH ( CH2OH ) -CH2-、-O-CH ( CH2OH ) -CH2-、 -CH ( N ( CH3) 2) -、-C6H4-0-、-C6H4-NH-、 -C6H4-CO-NH-、-C6H4-NH-CO-、c6h4-co-、-C6H4-CH2- -40- 200831611 、-CdrS-、環丙烷環、環丁烷環、環戊烷環、環己烷環 、環庚烷環、原菠烷環、金剛烷環、苯環、萘環、四氫萘 環、奠環、茚環、芴環、蒽環、菲環、菲那烯(Phenalene )環’ X5爲選自吡略環、咪u坐環、吡哇環、啦D定環、嘧口定 環、三嗪環、三唑環、吡嗪環、苯并咪唑環、間二氮茚環 、喹喔啉環、吖庚因環、二吖庚因環、萘啶環、菲嗪環、 酞嗪環。另外,X5之含氮芳香族雜環的碳原子,亦可具有 •I 鹵素原子及/或有機基之取代基,該有機基亦可含有氧原 子、硫原子、氮原子等之雜原子。 式〔4〕中更佳的乂3、义4及乂5之組合,係13爲選自 碳數1〜5之直鏈或支鏈烷基、環丙烷環、環丁烷環、環 戊烷環、環己烷環,X4爲選自單鍵、碳數1〜5之直鏈或 支鏈烷基、-0-、-NH-、-CO-O-、-O-CO-、-CO-NH-、 -NH-CO-、-CO-、-CH ( OH) -、-NH-CH2-、-S-CH2-、 -o-ch2-、-NH-CO-CH2·、-CO-CH2-、-CO-NH-CH2-、 • -NH-CH2-CH ( ch3 ) -、-S-CH2-CH ( CH3 )-、 -0-CH3-CH ( CH3 ) -、-NH-CO-CH2-CH ( CH3 )-、 -CH ( OH) -CH2-、-CH ( OH) -C2H4-、 -CH ( CH2〇H) -CH2-、-NH-CH ( CH2OH ) -CH2-、 -CO-NH-CH ( CH2OH) -CH2-、 -NH-CO-CH ( CH2〇H ) -CH2-、-CO-CH ( CH2OH ) -CH2- 、-S-CH ( CH2OH) -CH2-、-O-CH ( CH2OH) -CH2-、 -CH ( N ( CH3) 2) -、C6H4-0-、-C6H4-NH-、 -c6h4-co-nh-、-c6h4-nh-co-、-c6h4-co-、-c6h4-ch2- -41 - 200831611 、-C6H4-S-、環丙烷環、環丁烷環、環戊烷環、環己烷環 、環庚烷環、原菠烷環、金剛烷環、苯環、萘環、四氫萘 環、芴環、蒽環,X5爲選自吡咯環、咪唑環、吡唑環、吡 啶環、嘧啶環、噠嗪環、三嗪環、三唑環、吡嗪環、苯并 咪唑環、間二氮茚環。此外,&之含氮芳香族雜環的碳原 子’亦可具有鹵素原子及/或有機基,該有機基亦可含有 氧原子、硫原子、氮原子等之雜原子。 馨 式〔4〕中最佳的X3、X4及X5之組合,係爲選自 碳數1〜5直鏈或支鏈烷基、環丁烷環、環己烷環,爲 選自單鍵、-0-、-C0-0-、-0-C0-、-C0.NH·、 、-CH ( OH )-、苯環、萘環、芴環、蒽環,&爲選自吡 咯環、咪唑環、吡唑環、吡啶環、嘧啶環。另外,χ5之含 氮芳香族雜環的碳原子’亦可具有鹵素原子及/或有機基 之取代基,該有機基亦可含有氧原子、硫原子、氮原子等 之雜原子。 • 本發明所使用的特定胺化合物之具體例,如M1〜 Μ 1 5 6之化合物。 -42- 200831611 〔化 23〕-NH-CH2-CH(CH3)-, -S-CH2-CH(CH3)-, -0-CH3-CH(CH3)-, -NH-CO-CH2-CH(CH3)-, -CH (OH -CH2-, -CH(OH)-C2H4-, -CH(CH2OH)-CH2-, -NH-CH(CH2OH)-CH2-, -CO-NH-CH(CH2OH)-CH2-, -NH- CO-CH ( CH2OH ) -CH2-, -CO-CH ( CH2〇H ) -CH2- , -S-CH ( CH2OH ) -CH2-, -O-CH ( CH2OH ) -CH2-, -CH (N ( CH3) 2) -, -C6H4-0-, -C6H4-NH-, -C6H4-CO-NH-, -C6H4-NH-CO-, c6h4-co-, -C6H4-CH2--40- 200831611,- CdrS-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, raw spinane ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, ring opening, Anthracycline, anthracene, anthracene, anthracene ring, phenanthrene ring, and phenanene ring X5 are selected from the group consisting of a pyridyl ring, a silane ring, a pyrha ring, a D ring, a pyridazine ring, and a triazine ring. , a triazole ring, a pyrazine ring, a benzimidazole ring, a metadiazonium ring, a quinoxaline ring, a azepine ring, a dioxetane ring, a naphthyridine ring, a phenazine ring, a pyridazine ring. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of X5 may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. More preferably, the combination of 乂3, 义4 and 乂5 in the formula [4] is a linear or branched alkyl group selected from the group consisting of carbon atoms 1 to 5, a cyclopropane ring, a cyclobutane ring, and a cyclopentane. Ring, cyclohexane ring, X4 is a linear or branched alkyl group selected from a single bond, carbon number 1 to 5, -0-, -NH-, -CO-O-, -O-CO-, -CO -NH-, -NH-CO-, -CO-, -CH(OH)-, -NH-CH2-, -S-CH2-, -o-ch2-, -NH-CO-CH2·, -CO- CH2-, -CO-NH-CH2-, • -NH-CH2-CH(ch3)-, -S-CH2-CH(CH3)-, -0-CH3-CH(CH3)-, -NH-CO- CH2-CH(CH3)-, -CH(OH)-CH2-, -CH(OH)-C2H4-, -CH(CH2〇H)-CH2-, -NH-CH(CH2OH)-CH2-, -CO -NH-CH ( CH2OH) -CH2-, -NH-CO-CH ( CH2〇H ) -CH2-, -CO-CH ( CH2OH ) -CH2- , -S-CH ( CH2OH) -CH2-, -O -CH ( CH2OH) -CH2-, -CH ( N ( CH3) 2) -, C6H4-0-, -C6H4-NH-, -c6h4-co-nh-, -c6h4-nh-co-, -c6h4- Co-, -c6h4-ch2--41 - 200831611, -C6H4-S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, raw spinel ring, adamantane Ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, X5 is selected from pyrrole ring, microphone Ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, indolizine ring between the two. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of & may have a halogen atom and/or an organic group, and the organic group may also contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. The combination of X3, X4 and X5 which is the best in the formula [4] is selected from a linear or branched alkyl group having a carbon number of 1 to 5, a cyclobutane ring and a cyclohexane ring, and is selected from a single bond. -0-, -C0-0-, -0-C0-, -C0.NH·, , -CH(OH)-, benzene ring, naphthalene ring, anthracene ring, anthracene ring, & Imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring. Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of χ5 may have a substituent of a halogen atom and/or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. • Specific examples of the specific amine compound used in the present invention, such as a compound of M1 to Μ1 5 6 . -42- 200831611 〔化 23〕
M20M20
M32 M33 M34 -43- 200831611M32 M33 M34 -43- 200831611
h3c、0H3c, 0
-44- 、0200831611 化25〕 h3c、 M68 σ°-44- , 0200831611 25] h3c, M68 σ°
M73 NH2M73 NH2
M72M72
M76M76
NH2 M77 M78 NH2 F ch3NH2 M77 M78 NH2 F ch3
h3c〆H3c〆
M80 M79M80 M79
-45- 200831611 〔化26-45- 200831611 〔化26
M97M97
M101 M98 M99 M100 nh2 Cl F OH Λ rVCF3 Λ rv V u v nh2 ^nh2 M102 M103 M104 M105 cf3 h、,f3 ΗU、M101 M98 M99 M100 nh2 Cl F OH Λ rVCF3 Λ rv V u v nh2 ^nh2 M102 M103 M104 M105 cf3 h,,f3 ΗU,
ch3 M106 h3cCh3 M106 h3c
NH2 h2n M108NH2 h2n M108
M107 M109M107 M109
M113M113
M115 n H M116 /V. f 丫、OH [ NH2 N H M117M115 n H M116 /V. f 丫, OH [ NH2 N H M117
M118 h2n M119 M120 H 〇 Ml 22M118 h2n M119 M120 H 〇 Ml 22
N HN H
ΝΗ:Ή X:OH M123ΝΗ:Ή X:OH M123
N H M124 ύ M121 H h2u M125 46 200831611 〔化 27〕N H M124 ύ M121 H h2u M125 46 200831611 〔化 27〕
M126 NH2M126 NH2
M130M130
~NH2~NH2
CH3 N H H3C M133CH3 N H H3C M133
C CH3 o- M134 M135 M136C CH3 o- M134 M135 M136
OO
Η2Νχ/〇 po οςκ M152 M153Η2Νχ/〇 po οςκ M152 M153
、N 、CT、NH2 Ml 50 H3C^N、, N, CT, NH2 Ml 50 H3C^N,
O M151 M155O M151 M155
Mt56 較佳的化合物例如 M6〜M8、M10、M16〜M21、 M31 〜M36、M40〜M45、M47〜M57、M59〜M63、M68、M69 、M72 〜M82 、 M95 〜M98 、 M100 〜M103 、 M108 〜M125 、 Ml 28〜Ml 37、Ml 39〜M143、Ml 49 〜Ml 56。更佳者例如 -47- 200831611 M6 〜M8、 M16 〜M20、M32 〜M36、 M40、 M41 、M44、 M49 〜M54 、 M59〜M62 、 M68 、 M69 、 M75 〜M82 、 M100〜M103、M108〜M112、M114〜M116、M118〜M121、 Μ 125 ' Ml 34〜Ml 36、Ml 39、 Ml 40、 Ml 43 、 Ml 50、Preferred compounds of Mt56 are, for example, M6 to M8, M10, M16 to M21, M31 to M36, M40 to M45, M47 to M57, M59 to M63, M68, M69, M72 to M82, M95 to M98, M100 to M103, M108 to M125, Ml 28~Ml 37, Ml 39~M143, Ml 49~Ml 56. More preferably, for example, -47-200831611 M6 to M8, M16 to M20, M32 to M36, M40, M41, M44, M49 to M54, M59 to M62, M68, M69, M75 to M82, M100 to M103, M108 to M112, M114~M116, M118~M121, Μ125 'Ml 34~Ml 36, Ml 39, Ml 40, Ml 43 , Ml 50,
Ml 52〜Ml 56 ° <液晶配向處理劑> 本發明之液晶配向處理劑,通常係使上述(A )成分 之特定聚醯亞胺與(B )成分之特定胺化合物在有機溶劑 中混合製得。混合的特定胺化合物可以爲1種,亦可數種 倂用。 混合方法可使用使特定聚醯亞胺之前驅體的聚胺基酸 進行醯亞胺化的反應溶液(特定聚醯亞胺之溶液),惟通 常例如在使精製所得的特定聚醯亞胺之粉體溶解於有機溶 劑之溶液中,添加特定胺化合物的方法。此時所使用的有 機溶劑,只要是可使特定聚醯亞胺溶解的溶液即可,沒有 特別的限制。其具體例如下所述。 例如有N,N,-二甲基甲醯胺、N,N、二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-甲基己內酯、2-吡咯烷酮、N-乙基吡 咯烷酮、N-乙烯基吡咯烷酮、二甲基亞礪、四甲基尿素、 吡啶、二甲基颯、六甲基亞颯、γ-己內酯、1,3·二甲基-咪 唑二酮、二戊烯、乙基戊酮、甲基壬酮、甲基乙酮、甲基 異戊酮、甲基異丙酮、環己酮、碳酸乙二酯、碳酸丙二酯 、二直鏈聚醚、4_羥基-4-甲基-2-戊酮等。此等之溶劑亦 -48- 200831611 可2種以上混合使用。 使特定聚醯亞胺溶解於有機溶劑時,以促進特定聚醯 亞胺溶解爲目的時,亦可進行加熱。加熱的溫度過高時, 由於會使聚醯亞胺之分子量降低,故以溫度30〜100 °C較 佳’以50〜90 °C更佳。特定聚醯亞胺之溶液的濃度,沒有 特別的限制,爲容易與特定胺化合物均勻混合時,溶液中 之特定聚醯亞胺濃度以1〜20質量%較佳,以3〜1 5質量 %更佳,以3〜1 0質量%最佳。 特定胺化合物只要是可直接添加於溶劑可溶性聚醯亞 胺之溶液即可,在適當的溶劑中形成濃度0.1〜10質量% 、較佳者爲1〜7質量%溶液後予以添加較佳。該溶劑例如 上述溶劑可溶性聚醯亞胺之溶劑。 使特定聚醯亞胺與特定胺化合物在有機溶劑中,進行 加熱且混合、或於混合後進行加熱較佳。藉由加熱,增加 在液晶配向處理劑狀態下已鍵結的特定胺化合物與特定聚 醯亞胺之比例,且形成液晶配向膜時可更爲有效地進行電 合移動。上述加熱時之溫度,以10〜l〇〇°C較佳,以20〜 8 0 °C更佳。 特定胺化合物之添加量,就可更爲有效地得到本發明 之效果,且不會損害液晶配向處理劑之安全性而言,對1 莫耳量之特定聚醯亞胺中所含的羧基而言以〇.〇1〜2莫耳 倍較佳,更佳者爲〇.〇5〜1莫耳倍,最佳者爲0.08〜0.8 莫耳倍。 本發明之液晶配向處理劑,除特定聚醯亞胺、特定胺 -49- 200831611 化合物外,亦可含有其他成份之爲提高塗覆液晶配向處理 劑時之膜厚均勻性或表面平滑性的溶劑或化合物、爲提高 液晶配向膜與基板之密接性的化合物等。其他成份可以在 使特定聚醯亞胺與特定胺化合物進行混合的途中添加,亦 可於此等之混合溶液後予以添加。 爲提高膜厚均勻性或表面平滑性之溶劑的具體例,如 下所述。 例如,異丙醇、甲氧基甲基戊醇、甲基溶纖劑、乙基 溶纖劑、丁基溶纖劑、甲基溶纖劑乙酸酯、乙基溶纖劑乙 酸酯、丁基卡必醇、乙基卡必醇、乙基卡必醇乙酸酯、乙 二醇、乙二醇單乙酸酯、乙二醇單異丙醚、乙二醇單丁醚 、丙二醇、丙二醇單乙酸酯、丙二醇單甲醚、丙二醇-第 3-丁醚、二丙二醇單甲醚、二乙二醇、二乙二醇單乙酸酯 、二乙二醇二甲醚、二丙二醇單乙酸酯單甲醚、二丙二醇 單甲醚、二丙二醇單乙醚、二丙二醇單乙酸酯單乙醚、二 丙二醇單丙醚、二丙二醇單乙酸酯單丙醚、3 -甲基-3 -甲氧 基丁基乙酸酯、三丙二醇甲醚、3-甲基-3-甲氧基丁醇、二 異丙醚、乙基異丁醚、二異丁烯、戊基乙酸酯、丁基丁酸 酯、丁醚、二異丁酮、甲基環己烯、丙醚、二己醚、正己 烷、正戊烷、正辛烷、二乙醚、乳酸甲酯、乳酸乙酯、醋 酸甲酯、醋酸乙酯、醋酸正丁酯、醋酸丙二醇單乙醚、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、甲氧 -50 - 200831611 基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧 基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇_ 1-單甲醚-2 -乙酸酯、丙二醇-1-單乙醚-2 -乙酸酯、二丙二 醇、2- ( 2-乙氧基丙氧基)丙醇、乳酸甲酯、乳酸乙酯、 乳酸正丙酯、乳酸正丁酯、乳酸異戊酯等具低表面張力之 溶劑等。 此等之溶劑,可使用1種或數種混合。使用上述之溶 劑時,以液晶配向處理劑中所含的溶劑全體之5〜80質量 %較佳,以20〜60質量%更佳。 爲提高膜厚均勻性或表面平滑性之化合物’例如氟系 界面活性劑、聚矽氧烷系界面活性劑、非離子系界面活性 劑等。 更具體而言,例如耶夫頓布(譯音)EF301、EF3 03、 EF352 (頓肯姆布羅拉谷茲(譯音)公司製)、梅卡法谷 (譯音)F171、F173、R-30(大日本油墨公司製)、夫羅 拉頓(譯音)FC430、FC431 (住友3M公司製)、阿撒西 卡頓(譯音)AG710、撒夫龍(譯音)S-382、SC101、 SC102、SC103、SC104、SC10 5、SC106(旭玻璃公司製) 等。此等界面活性劑之使用比例,對1 00質量份液晶配向 處理劑中所含的(A)成分而言,以0.01〜2質量份較佳 ,以0 · 0 1〜1質量份更佳。 爲提高液晶配向膜與基板之密接性的化合物之具體例 ,如下述所示含官能性矽烷之化合物或含環氧基之化合物 -51 - 200831611 例如3-胺基丙基三甲氧基矽烷、3-胺基 矽烷、2 -胺基丙基三甲氧基矽烷、2 -胺基丙 烷、N- ( 2-胺基乙基)-3-胺基丙基三甲氧基 胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、 甲氧基矽烷、3 -脲基丙基三乙氧基矽烷、N_: 胺基丙基三甲氧基矽烷、N -乙氧基羰基- 3-氧基矽烷、N-三乙氧基甲矽烷基丙基三乙三 基甲矽烷基丙基三乙三胺、10 -三甲氧基甲 三氮雜癸烷、10-三乙氧基甲矽烷基-1,4,7-三 三甲氧基甲矽烷基-3,6-二氮雜壬基乙酸酯、 矽烷基-3,6-二氮雜壬基乙酸酯、N-苯甲基-甲氧基矽烷、N-苯甲基-3-胺基丙基三乙氧 基-3-胺基丙基酸甲氧基矽烷、N-苯基-3-胺 基矽烷、N-雙(氧化乙烯)-3-胺基丙基三 N-雙(氧化乙烯)-3-胺基丙基三乙氧基矽 環氧丙醚、聚乙二醇二環氧丙醚、丙二醇二 丙二醇二環氧丙醚、聚丙二醇二環氧丙醚、 丙醚、1,6·己二醇二環氧丙醚、丙三醇二環 二溴化新戊醇二環氧丙醚、1,3,5,6 -四環氧 醇、N,N,N’,N’-四環氧丙基-m-二甲苯二胺、 二環氧丙基胺基甲基)環己烷、N,N,N,,N’ 4,4’-二胺基二苯基甲烷等。 添加此等化合物時,對1 00質量份液晶 所含的特定聚醯亞胺成分而言,以0.1〜30 丙基三乙氧基 基三乙氧基砍 砂院、N - ( 2 -3 -脲基丙基三 乙氧基羰基-3-胺基丙基三乙 胺、N-三甲氧 矽烷基-1,4,7 · 氮雜癸烷、9 -9-三乙氧基甲 3 -胺基丙基三 基矽烷、N-苯 基丙基酸乙氧 甲氧基矽烷、 烷、乙二醇二 環氧丙醚、三 新戊醇二環氧 :氧丙醚、2,2-丙基-2,4-己二 1,3-雙(N,N--四環氧丙基- 配向處理劑中 質量份較佳’ -52- 200831611 以1〜2 0質量份更佳。未達0 · 1質量份時,無法達到提高 密接性之效果,大於3 0質量份時’液晶之配向性變得不 佳。 於本發明之液晶配向處理劑中,除上述外,在不會損 害本發明效果之範圍內,亦可添加特定聚醯亞胺以外之聚 合物成分、或使液晶配向膜之介電常數或導電性等之電氣 變化爲目的之介電體或導電物質,以及以提高形成液晶配 向膜時之膜硬度或緻密度爲目的的交聯性化合物。 本發明之液晶配向處理劑中固成分之濃度,可藉由目 的之液晶配向膜的膜厚度予以適當改變,惟就形成沒有缺 陷的塗膜、且可得作爲液晶配向膜之適當膜厚而言,以1 〜2 0質量%較佳,以2〜1 0質量%更佳。 <液晶配向膜•液晶顯示元件> 本發明之液晶配向處理劑,可使用於塗覆於基板上予 以燒成後,進行摩擦處理或以光照射等之配向處理,或在 垂直配向用途等時沒有經過配向處理,作爲液晶配向膜使 用。此時,所使用的基板只要是透明性高的基板即可,沒 有特別的限制,可使用玻璃基板、丙烯酸基板或聚碳酸酯 基板等之塑膠基板等。特別是使用爲形成液晶驅動時之 ΙΤΟ電極等的基板時,就製程簡單化而言較佳。而且,反 射型液晶顯示元件,可僅在一側基板上且使用矽晶圓等之 不透明物,此時之電極亦可使用氧化鋁等之使光反射的材 料0 -53- 200831611 液晶配向處理劑之塗覆方法,沒有特別的限制’在工 業上一般有藉由篩網印刷、離線印刷、可撓性印刷、噴墨 等進行的方法。其他塗覆方法有浸漬、輥塗覆、隙縫塗覆 、旋轉器等,視其目的而定使用此等。 使液晶配向處理劑塗覆於基板後之燒成,可藉由熱板 等之加熱方法、於50〜200°C、較佳者爲80〜15(TC下使溶 劑蒸發,形成塗膜。燒成後塗膜之厚度,過厚時就液晶顯 φ 示元件之消耗電力而言極爲不利,過薄時會降低液晶顯示 元件之信賴性,以5〜3 0 0 n m較佳,以1 0〜1 0 0 n m。使液 晶進行水平配向或傾斜配向時,使燒成後之塗膜以摩擦或 偏光紫外線照射等予以處理。 本發明之液晶顯示元件,係爲藉由上述方法由本發明 之液晶配向劑製得附有液晶配向膜之基板後,以習知的方 法製作液晶晶胞,形成液晶顯示元件。 以製作液晶晶胞爲例時,係使用形成有1對液晶配向 # 膜之基板,在一側基板之液晶配向膜上散佈間距器,且以 液晶配向膜面爲內側,使另一側基板貼合,減壓注入液晶 _ 予以密封的方法,或在散佈有間距器之液晶配向膜面上滴 下液晶後,使基板貼合予以密封的方法等。此時間距器之 厚度,以1〜3 0 μπι較佳’以2〜10卞111更佳。 如上所述,使用本發明之液晶配向處理劑所製作的液 晶顯示元件,係爲信賴性優異者’可利用於大畫面且高精 細的液晶電視等。 -54- 200831611 【實施方式】 於下述中,以實施例爲例更詳細地說明本發明,惟本 發明不受此等所限制。 〔實施例〕 實施例中所使用的簡稱,如下所述。Ml 52 to Ml 56 ° <Liquid Crystal Alignment Treatment Agent> The liquid crystal alignment treatment agent of the present invention is usually obtained by mixing a specific polyimine of the above component (A) with a specific amine compound of the component (B) in an organic solvent. be made of. The specific amine compound to be mixed may be one type or several types. The mixing method may use a reaction solution (a solution of a specific polyimine) which is subjected to hydrazylation of a polyamino acid of a specific polyimine precursor, but usually, for example, a specific polyimine obtained by refining A method in which a powder is dissolved in a solution of an organic solvent and a specific amine compound is added. The organic solvent to be used at this time is not particularly limited as long as it is a solution which can dissolve a specific polyimine. This is specifically described below. For example, there are N,N,-dimethylformamide, N,N, dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactone, 2-pyrrolidone, N-ethyl Pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-caprolactone, 1,3-dimethyl-imidazoledione, Dipentene, ethyl pentanone, methyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, cyclohexanone, ethylene carbonate, propylene carbonate, di-linear polyether, 4-hydroxy-4-methyl-2-pentanone and the like. These solvents are also used in combination of -48- 200831611. When a specific polyimine is dissolved in an organic solvent, heating may be performed for the purpose of promoting dissolution of a specific polyimine. When the heating temperature is too high, the molecular weight of the polyimine is lowered, so that the temperature is preferably 30 to 100 ° C, more preferably 50 to 90 ° C. The concentration of the solution of the specific polyimine is not particularly limited. When it is easily mixed with a specific amine compound, the concentration of the specific polyimine in the solution is preferably from 1 to 20% by mass, preferably from 3 to 15% by mass. More preferably, it is preferably 3 to 10% by mass. The specific amine compound may be a solution which can be directly added to the solvent-soluble polyimine, and is preferably added in a suitable solvent to a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent is, for example, a solvent of the above solvent-soluble polyimine. It is preferred to heat and mix the specific polyimine with a specific amine compound in an organic solvent or to heat it after mixing. By heating, the ratio of the specific amine compound bonded to the specific polyimine in the state of the liquid crystal alignment agent is increased, and the electromigration movement can be performed more efficiently when the liquid crystal alignment film is formed. The temperature at the time of the above heating is preferably 10 to 10 ° C, more preferably 20 to 80 ° C. The addition amount of the specific amine compound can more effectively obtain the effect of the present invention without impairing the safety of the liquid crystal alignment treatment agent, and the carboxyl group contained in the specific polyimine of 1 mole. 〇 〇 〇 〜 1 ~ 2 Moer times better, better is 〇. 〇 5 ~ 1 Mo, the best is 0.08 ~ 0.8 Mo Er times. The liquid crystal alignment treatment agent of the present invention may contain, in addition to the specific polyimine and the specific amine-49-200831611 compound, a solvent which improves the film thickness uniformity or surface smoothness when coating the liquid crystal alignment treatment agent. Or a compound, a compound which improves the adhesiveness of a liquid crystal alignment film and a board|substrate. Other ingredients may be added during the mixing of the specific polyimine and the specific amine compound, or may be added after mixing the solutions. Specific examples of the solvent for improving the film thickness uniformity or the surface smoothness are as follows. For example, isopropanol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Acetate, propylene glycol monomethyl ether, propylene glycol - 3-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetic acid Ester monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxy Butyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate , butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate Ester, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropane Ethyl acetate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methoxy-50 - 200831611 -2- Propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol 1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate A solvent having a low surface tension such as n-propyl lactate, n-butyl lactate or isoamyl lactate. These solvents may be used in one or a mixture of several. When the above-mentioned solvent is used, it is preferably 5 to 80% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent, and more preferably 20 to 60% by mass. A compound which is used to improve film thickness uniformity or surface smoothness, for example, a fluorine-based surfactant, a polyoxyalkylene-based surfactant, a nonionic surfactant, or the like. More specifically, for example, Yevtton cloth (transliteration) EF301, EF3 03, EF352 (made by Don Kembroke Guz (trans) company), Mekkafa Valley (transliteration) F171, F173, R-30 (large Japan Ink Company), Fraradon FC430, FC431 (manufactured by Sumitomo 3M), Asa Kayton (AG), Safron (Sound) S-382, SC101, SC102, SC103, SC104, SC10 5, SC106 (made by Asahi Glass Co., Ltd.), etc. The use ratio of the surfactants is preferably 0.01 to 2 parts by mass, more preferably 0. 01 to 1 part by mass, based on the component (A) contained in 100 parts by mass of the liquid crystal alignment agent. Specific examples of the compound for improving the adhesion between the liquid crystal alignment film and the substrate are as follows: a functional decane-containing compound or an epoxy group-containing compound -51 - 200831611, for example, 3-aminopropyltrimethoxydecane, 3 -Aminodecane, 2-aminopropyltrimethoxydecane, 2-aminopropane, N-(2-aminoethyl)-3-aminopropyltrimethoxyaminoethyl)-3- Aminopropylmethyldimethoxydecane, methoxydecane, 3-ureidopropyltriethoxydecane, N_: aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-oxo Baseline, N-triethoxymethanealkylpropyltriethylenetrimethylformamidopropyltriethylenetriamine, 10-trimethoxymethyltriazadecane, 10-triethoxymethylidene- 1,4,7-tris-trimethoxycarbamido-3,6-diazaindolyl acetate, decyl-3,6-diazaindolyl acetate, N-benzyl- Methoxydecane, N-benzyl-3-aminopropyltriethoxy-3-aminopropyl methoxy decane, N-phenyl-3-aminodecane, N-bis (oxidation) Ethylene)-3-aminopropyltri-N-bis(ethylene oxide)-3-aminopropyltriethoxyphosphonium oxide Propyl ether, polyethylene glycol diglycidyl ether, propylene glycol dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, propyl ether, 1,6 hexanediol diglycidyl ether, glycerol II Cyclobromonated neopentyl diglycidyl ether, 1,3,5,6-tetraepoxy alcohol, N,N,N',N'-tetraepoxypropyl-m-xylenediamine, two Epoxypropylaminomethyl)cyclohexane, N,N,N,,N' 4,4'-diaminodiphenylmethane, and the like. When such a compound is added, the specific polyamidiene component contained in 100 parts by mass of the liquid crystal is 0.1 to 30 propyl triethoxytriethoxy chopping sand, N - ( 2 -3 - Ureidopropyltriethoxycarbonyl-3-aminopropyltriethylamine, N-trimethoxydecyl-1,4,7-azanonane, 9-9-triethoxymethyl-3-amine Propyltriyldecane, N-phenylpropyl acid ethoxymethoxydecane, alkane, ethylene glycol diglycidyl ether, trisinopentyl epoxide: oxypropyl ether, 2,2-propyl -2,4-hexanedi1,3-1,3-(N,N-tetraepoxypropyl-aligning treatment agent preferably having a mass part of -52-200831611 more preferably 1 to 20 parts by mass. When the amount is 1 part by mass, the effect of improving the adhesion is not obtained, and when it is more than 30 parts by mass, the alignment property of the liquid crystal becomes poor. In the liquid crystal alignment treatment agent of the present invention, the present invention is not impaired except the above. Within the range of the effect, a polymer component other than the specific polyimine or a dielectric or conductive substance for the electrical change of the dielectric constant or conductivity of the liquid crystal alignment film may be added, and the liquid crystal may be formed to be improved. Match The cross-linking compound for the purpose of film hardness or density in the film. The concentration of the solid component in the liquid crystal alignment agent of the present invention can be appropriately changed by the film thickness of the intended liquid crystal alignment film, but no defect is formed. The coating film is preferably 1 to 20% by mass, more preferably 2 to 10% by mass, as the appropriate film thickness of the liquid crystal alignment film. <Liquid alignment film/liquid crystal display element> The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being subjected to baking treatment by a substrate, followed by rubbing treatment or alignment treatment such as light irradiation, or in the case of vertical alignment use or the like without undergoing alignment treatment. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, an acrylic substrate or a polycarbonate substrate can be used. In the case of a substrate such as an electrode, it is preferable in terms of simplification of the process, and the reflective liquid crystal display element can be used only on one substrate and an opaque object such as a germanium wafer. In this case, the electrode may be a material such as alumina or the like which reflects light. The method of coating the liquid crystal alignment agent is not particularly limited. In the industry, it is generally screen-printed, off-line, and A method of performing flexographic printing, inkjet, etc. Other coating methods include dipping, roll coating, slit coating, rotator, etc., depending on the purpose, etc. After the liquid crystal alignment treatment agent is applied to the substrate The baking may be carried out by a heating method such as a hot plate at 50 to 200 ° C, preferably 80 to 15 (the solvent is evaporated under TC to form a coating film. The thickness of the coating film after firing is too thick) The power consumption of the liquid crystal display element is extremely unfavorable. When it is too thin, the reliability of the liquid crystal display element is lowered, preferably 5 to 300 nm, and 10 to 100 nm. When the liquid crystal is subjected to horizontal alignment or oblique alignment, the coating film after firing is treated by rubbing or polarized ultraviolet irradiation or the like. In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the above method, and a liquid crystal cell is produced by a conventional method to form a liquid crystal display element. For example, when a liquid crystal cell is produced, a substrate on which a pair of liquid crystal alignment films are formed is used, and a spacer is spread on a liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is inside, and the other substrate is pasted. The liquid crystal is injected under reduced pressure _ a method of sealing, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface on which a spacer is dispersed, and the substrate is bonded and sealed. At this time, the thickness of the spacer is preferably from 1 to 30 μm, preferably from 2 to 10,111. As described above, the liquid crystal display element produced by using the liquid crystal alignment agent of the present invention is excellent in reliability, and can be used for a large-screen, high-definition liquid crystal television or the like. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. [Examples] The abbreviations used in the examples are as follows.
(四羧酸二酐) BODA:二環〔3,3,0〕辛烷-2,4,6,8-四羧酸二酐 CBDA: 1,2,3,4-環丁烷四羧酸二酐 TDA ·· 3,4-二羧基-1,2,3,4-四氫-1-萘琥珀酸二酐 〔化 28〕(tetracarboxylic dianhydride) BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutane tetracarboxylic acid Dihydride TDA ·· 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (28)
(二胺) p-PDA : p-苯二胺 PCH: 1,3-二胺基-4-〔4-(4-庚基環己基)苯氧基〕 苯 DBA : 3,5-二胺基苯甲酸 DADPA : 4,4,-二胺基二苯胺 -55- 200831611(Diamine) p-PDA : p-phenylenediamine PCH: 1,3-diamino-4-[4-(4-heptylcyclohexyl)phenoxy]benzene DBA : 3,5-diamino DADPA benzoic acid : 4,4,-diaminodiphenylamine-55- 200831611
DBA DADPA (特定胺化合物) 3 - A Μ P · 3 -胺基甲基卩比D定 AEP : 4- ( 2-胺基乙基)吡啶 API : 1- ( 3-胺基丙基)咪唑 4-AMP : 4-胺基甲基吡啶 2AMMP : 2-(胺基甲基)-5-甲基吡嗪 〔化 30〕DBA DADPA (specific amine compound) 3 - A Μ P · 3 -aminomethyl hydrazine ratio D-defined AEP : 4-(2-aminoethyl)pyridine API : 1-( 3-aminopropyl)imidazole 4 -AMP : 4-aminomethylpyridine 2AMMP : 2-(aminomethyl)-5-methylpyrazine [30]
(比較化合物) MI : 2-甲基咪唑 -56- 200831611(Comparative compound) MI : 2-methylimidazole -56- 200831611
Py :啦b定 VPy : 2-乙烯基吡啶Py : 啦b VPy : 2-vinyl pyridine
ΑΡΜΑ : N- ( 3-胺基丙基)-N-甲基苯胺 ΑΡ : 3-胺基吡啶 ΗΑ :正己胺ΑΡΜΑ : N-( 3-aminopropyl)-N-methylaniline ΑΡ : 3-aminopyridine ΗΑ : n-hexylamine
H2N-C6H13H2N-C6H13
HA (有機溶劑)HA (organic solvent)
NMP : N-甲基-2-吡咯烷酮 BCS : 丁基溶纖劑 GBL : γ-丁內酯 <聚醯亞胺之分子量測定> 合成例之聚醯亞胺的分子量,係使用新修(譯音)科 學公司製常溫凝膠滲透色層分析法(GPC )裝置(SScNMP : N-methyl-2-pyrrolidone BCS : butyl cellosolve GBL : γ-butyrolactone < molecular weight determination of polyimine > The molecular weight of the polyimine of the synthesis example, using a new repair Scientific company system room temperature gel permeation chromatography (GPC) device (SSc
7200) 、Shodex 公司製柱(KD- 803、KD805 ),inY F述予 以測定。7200), Shodex company column (KD-803, KD805), inY F is described for measurement.
柱溫度:5 0 °C 溶離液:N,N,-二甲基甲醯胺(以溴化鋰〜外八 e物( -57- 200831611Column temperature: 50 °C Dissolution: N, N, - dimethylformamide (with lithium bromide ~ outer eight e (-57- 200831611
LiBr-H20 )爲30mmol/L、磷酸•無水結晶(〇_磷酸)爲 30mmol/L、四氫呋喃(THF)爲10ml/L)作爲添加劑) 流速:l.OmL /分 檢量線作成用標準試樣:東索公司製TSK標準聚氧化 乙烯(分子量約 9000,000、 150,000、 100,000、 3〇〇〇〇) 、及聚合物拉伯拉頓里(譯音)公司製聚乙二醇 量約 12,000、4,000、1,000)。 <醯亞胺化之測定> 合成例中聚醯亞胺之醯亞胺化率,如下述予以沏(定。 使2 Omg聚醯亞胺粉末加入NMR試樣管(草野科學公司製 NMR試樣管啓動機 φ 5 ),添加0.53ml重氫化二甲基亞 礪(DMSO-d5、0.05%TMS混合品),施予超音波予以完 全溶解。使該溶液以日本電子迪塔姆(譯音)公司製NMR 測定器(INW-ECA500 )測定500MHz之質子NMR。醯亞 Φ 胺化率係以來自在醯亞胺化前後沒有變化的構造之質子作 爲基準質子予以決定,使用該質子之波峰累計値、與來自 . 在9.5〜lO.Oppm附近出現的胺基酸之NH基的質子波峰累 計値,藉由下述式求取。 醯亞胺化率(% ) = ( · x/y ) X 1 00 於上述式中,x係爲來自胺基酸之NH基的質子波峰 累計値,y係爲來自基準質子之波峰累計値,α係爲對i -58- 200831611 個聚胺基酸(醯亞胺化率爲〇%)時胺基酸之NH基的質子 而言基準質子之個數比例。 <羧基量之求取方法> 藉由上述記載的方法求取。 (合成例1 ) 使 BODA ( 1 6.9g、68mmol ) 、p - P D A ( 6.8 g、6 3 mm ο 1 )、PCH(10.3g、27mmol)在 NMP(lOO.lg)中混合, 在4 0 °C下進行反應3小時後,加入c B D A ( 4 · 1 g、2 1 mm o 1 )與NMP ( 5 2.2g ),在40°C下進行反應3小時,製得聚 醯胺酸溶液。在該聚醯胺酸溶液(1 3 0.3 g )中加入NMP, 稀釋成6質量%後,加入醋酸酐(1 5 · 6 g )、吡啶(1 2 · 1 g )作爲醯亞胺化觸媒,在80 °C下進行反應3小時。使該反 應溶液投入甲醇(1 600ml )中,濾別所得的沉澱物。使該 沉澱物以甲醇洗淨,在1 00 °C下進行減壓乾燥,製得聚醯 亞胺粉末(A)。該聚醯亞胺之醯亞胺化率爲54%,數平 均分子量爲18,300,重量平均分子量爲45,300。該聚醯亞 胺之羧基量,對重複單位而言爲0.92個。 (合成例2) 使 BODA ( 16.9g、68mmol) 、p-PDA ( 6.8g、63mmol )、PCH ( 10.3g、2 7 mmol )在 NMP ( 100· 0g )中混合, 在40°C下進fT反應3小時後’加入CBDA(4.1g、21mmol -59- 200831611 )與NMP ( 52.2g),在40 °C下進行反應3小時,製得聚 醯胺酸溶液。在該聚醯胺酸溶液(55.4g )中加入NMP, 稀釋成6質量%後,加入醋酸酐(2.7g )、吡啶(2.1g ) 作爲醯亞胺化觸媒,在70 °C下進行反應1小時。使該反應 溶液投入甲醇(660ml )中,濾別所得的沉澱物。使該沉 澱物以甲醇洗淨,在100 °C下進行減壓乾燥,製得聚醯亞 胺粉末(B)。該聚醯亞胺之醯亞胺化率爲25%,數平均 分子量爲19,500,重量平均分子量爲47,800。該聚醯亞胺 之羧基量,對重複單位而言爲1.50個。 (合成例3 ) 使 BODA ( 1 50.1 g、600mmol ) 、DBA ( 60.9g、 400mmol ) 、PCH ( 152.2g、400mmol )在 NMP ( 1290g) 中混合,在80°C下進行反應5小時後,加入CBDA ( 38.8g 、198mmol )與NMP ( 3 20g ),在40 °C下進行反應3小時 ,製得聚醯胺酸溶液。在該聚醯胺酸溶液(600.2g )中加 入Ν Μ P,稀釋成6質量%後,加入醋酸醉(6 3 · 9 g )、吡D定 (49.6g)作爲醯亞胺化觸媒,在80°C下進行反應3小時 。使該反應溶液投入甲醇(7700ml)中,濾別所得的沉澱 物。使該沉澱物以甲醇洗淨,在1 00°C下進行減壓乾燥, 製得聚醯亞胺粉末(C)。該聚醯亞胺之醯亞胺化率爲 57%,數平均分子量爲23,000,重量平均分子量爲80,200 。該聚醯亞胺之羧基量,對重複單位而言爲1 . 3 6個。 -60 - 200831611 (合成例4) 使 BODA ( 50.1g、600mmol ) 、DBA ( 60.9g、 400mmol ) 、PCH ( 152.2g、400mmol )在 NMP ( 1 290g ) 中混合,在80°C下進行反應5小時後,加入CBDA ( 38.8g 、198mmol )與NMP ( 320g ),在4 0 °C下進行反應3小時 ,製得聚醯胺酸溶液。在該聚醯胺酸溶液(30O.lg )中加 入NMP,稀釋成6質量%後,加入醋酸酐(32.0g)、吡啶 φ ( 24.8g)作爲醯亞胺化觸媒,在90 °C下進行反應2.5小時 。使該反應溶液投入甲醇(3900ml )中,濾別所得的沉澱 物。使該沉澱物以甲醇洗淨,在1 〇〇°C下進行減壓乾燥, 製得聚醯亞胺粉末(D)。該聚醯亞胺之醯亞胺化率爲 69%,數平均分子量爲22,700,重量平均分子量爲69,3 00 。該聚醯亞胺之羧基量,對重複單位而言爲1.12個。 (合成例5) 使 BODA ( 150.lg ' 600mmol) 、DBA ( 60.9g、 400mmol ) 、PCH ( 152.2g、4 0 Ommol )在 NMP ( 1 2 9 0 g ) 中混合,在80°C下進行反應5小時後,加入CBDA ( 3 8.8g 、1 98mmol )與NMP ( 3 20g ),在40°C下進行反應3小時 ,製得聚醯胺酸溶液。在該聚醯胺酸溶液(101.2g )中加 入NMP,稀釋成6質量%後,加入醋酸酐(21.3g)、吡啶 (16.5g)作爲醯亞胺化觸媒,在90°C下進行反應3小時 。使該反應溶液投入甲醇(1 300ml )中,濾別所得的沉澱 物。使該沉澱物以甲醇洗淨,在1 00°C下進行減壓乾燥’ -61 - 200831611 製得聚醯亞胺粉末(E)。該聚醯亞胺之醯亞胺化率爲 81%,數平均分子量爲20,400,重量平均分子量爲63, 。該聚醯亞胺之羧基量,對重複單位而言爲〇.88個。 (合成例6 ) 使 BODA ( 16.0g、64mmol ) 、DAD PA ( H*9g 60mmol ) 、PCH ( 9.7g、26mmol)在 NMP ( 126.4g)中混 φ 合,在40°C下進行反應3小時後,加入CBDA ( 3.8g、 19mmol)與NMP(40g),在40°C下進行反應3小時’製 得聚醯胺酸溶液。在該聚醯胺酸溶液(5 〇. 3 g )中加入 NMP,稀釋成4質量%後,加入醋酸酐(5.0g )、吡卩定( 3.9g)作爲醯亞胺化觸媒,在50°C下進行反應2小時。使 該反應溶液投入甲醇(9 1 〇ml )中,濾別所得的沉澱物。 使該沉澱物以甲醇洗淨,在1〇〇°C下進行減壓乾燥’製得 聚醯亞胺粉末(F)。該聚醯亞胺之醯亞胺化率爲25% ’ φ 數平均分子量爲22,200,重量平均分子量爲69,000。該聚 醯亞胺之羧基量,對重複單位而言爲1.50個。 (合成例7) 使 BODA ( 7.5g、3 0mmol ) 、DADPA ( 1.6g、 8.0 m m ο 1 ) 、DBA ( 2.4g、 1 6mmol ) 、PCH ( 6.1g、 16mmol )在NMP ( 5 3.2g )中混合,在40°C下進行反應3 小時後,力口入 CBDA(1.9g、lOmmol)與 NMP(25g), 在40°C下進行反應3小時,製得聚醯胺酸溶液。在該聚醯 -62 - 200831611 胺酸溶液(60.4g )中加入NMP,稀釋成5質量%後,加入 醋酸酐(6 · 3 g )、吡啶(4 · 9 g )作爲醯亞胺化觸媒,在 90°C下進行反應2小時。使該反應溶液投入甲醇(8 80ml )中,濾別所得的沉澱物。使該沉澱物以甲醇洗淨,在 1 0 0 °C下進行減壓乾燥,製得聚醯亞胺粉末(〇 )。該聚醯 亞胺之醯亞胺化率爲51%,數平均分子量爲21,100,重量 平均分子量爲64,000。該聚醯亞胺之羧基量,對重複單位 而言爲1.38個。 (合成例8) 使 TDA(9.0g、30mmol) 、DBA(3.2g、21 mmo 1 )、 p-PDA(1.0g、9.0mmol)在 NMP(74.7g)中混合,在室 溫下進行反應24小時,製得聚醯胺酸溶液。在該聚醯胺 酸溶液(80.0g )中加入NMP,稀釋成6質量%後,加入醋 酸酐(2 9 · 1 g )、吡啶(1 3 · 5 g )作爲醯亞胺化觸媒,在 3 5 °C下進行反應3小時。使該反應溶液投入甲醇(7 i 〇ml )中,濾別所得的沉澱物。使該沉澱物以甲醇洗淨,在 1 00°C下進行減壓乾燥,製得聚醯亞胺粉末(Η )。該聚驢 亞胺之醯亞胺化率爲91%,數平均分子量爲ιυοο,重量 平均分子量爲20570 0。該聚醯亞胺之羧基量,對重複單位 而言爲0.88個。 (實施例1 ) 藉由在以合成例1所得的聚醯亞胺粉末(a) ( 7.4g -63- 200831611 )中加入NMP(41.9g),在80 °C下進行攪拌40小 溶解。在該溶液中加入3_AMP之7.5 14.8g )(作爲 3-AMP、l.llg) 、NMP(3.7g)、 55.5g),在50°C下進行攪拌15小時’製得液晶配 劑(1 )。 <液晶晶胞之製作> 使以上述所得的液晶配向處理劑(1 )旋轉塗 ITO電極之玻璃基板上,在80 °C之熱板上進行乾燥 後,以2 1 0°C之熱風循環式烤箱中進行燒成1小時 膜厚1 OOnm之液晶配向膜。使用2張該附液晶配向 板,在其中1張之液晶配向膜上散佈6·μιη之間距器 其上印刷密封劑,予以貼合後,使密封劑硬化,製 胞。在該空晶胞中藉由減壓注入法注入液晶ML C-梅魯谷(譯音)•日本公司製),使注入口密封, 列型液晶晶胞。 使該液晶晶胞以偏光顯微鏡觀察時,液晶均勻 配向,沒有配向缺陷情形。 <電壓保持率之評估> 在上述所製作的液晶晶胞上,在80°C之溫度 4V電壓60μδ,測定16.67ms後、及166 7 ms後之電 算保持多少電壓作爲電壓保持率。結果,16.67ms 保持率爲97.6%,1 667ms之電壓保持率爲67.3%。 時予以 溶液( BCS ( 向處理 覆於附 5分鐘 ,製作 膜之基 後,於 作空晶 6608 ( 製得向 地垂直 下施加 壓,計 之電壓 -64- 200831611 而且,測定係使用東洋迪谷尼卡(譯音)公司製 VHR-1電壓保持率測定裝置,以 Voltage : ±4V,Pulse Width: 60ps,Flame Period: 16.67ms 或 1667ms 之設定 予以測定。 <殘留電荷緩和之評估> 在上述電壓保持率測定後之液晶晶胞上,施加直流電 壓10V、30分鐘,產生短路情形1秒鐘後,測定1 800秒 間在液晶晶胞內產生的電位。此時之電位變化如第1圖所 示。結果,短路後50秒後之殘留電荷爲3.1 9V,1 000秒 後之殘留電荷爲0.25V。而且,測定係使用東洋迪谷尼卡 (譯音)公司製6254型液晶物性評估裝置。 <高溫放置後之評估> 使上述測定完成的液晶晶胞在設定於1 00 °C之恆溫槽 中放置7日後,進行相同的測定。結果,16.67ms之電壓 保持率爲97.8%,1 667ms之電壓保持率爲67.2%,50秒後 之殘留電荷爲3.41 V,1 000秒後之殘留電荷爲0.46V。 (實施例2〜實施例1 8 ) 如下所述調製液晶配向處理劑(2 )〜(1 8 ),與實 施例1相同地製作液晶晶胞,進行評估。於全部之晶胞中 ,液晶均勻地垂直配向,沒有配向缺陷情形。評估結果如 下述之表1及表2記載。 -65- 200831611 (實施例2 ) 除使用以合成例2所得的聚醯亞胺粉末(B )外,與 實施例1相同地調製,製得液晶配向處理劑(2)。 (實施例3 ) 除使用以合成例3所得的聚醯亞胺粉末(C ),在 7〇°C下進行攪拌40小時予以溶解外,與實施例1相同地 調製,製得液晶配向處理劑(3 )。 (實施例4) 藉由在以合成例3所得的聚醯亞胺粉末(C ) ( 5.4g )中加入NMP ( 30.6g ),在70°C下進行攪拌40小時予以 溶解。在該溶液中加入3-AMP之1〇質量%NMP溶液( 5.4g)(作爲 3-AMP、0.38g) 、NMP(8.1g) 、BCS( 4 0.5g),在50 °C下進行攪拌15小時,製得液晶配向處理 劑(4 )。 (實施例5 ) 藉由在以合成例3所得的聚醯亞胺粉末(C ) ( 5.4g )中加入NMP ( 30.6g),在70Ό下進行攪拌40小時予以 溶解。在該溶液中加入3-ΑΜΡ之7質量%ΝΜΡ溶液(5.4g )(作爲 3-AMP、〇.38g) 、NMP ( 8.1g) 、BCS ( 40.5g ),在50°C下進行攪拌1 5小時,製得液晶配向處理劑(5 -66- 200831611 (實施例6 ) 藉由在以合成例3所得的聚醯亞胺粉末(C ) ( 7.4g )中加入NMP ( 41.9g),在70°C下進行攪拌40小時予以 溶解。在該溶液中加入3-AMP之5質量%NMP溶液(7.4g )(作爲 3-AMP、0.37g) 、NMP(ll.lg) 、BCS(55.5g ),在5 0 °C下進行攪拌1 5小時,製得液晶配向處理劑(6 (實施例7) 藉由在以合成例3所得的聚醯亞胺粉末(C )( 7.4g )中加入NMP ( 41.9g ),在70°C下進行攪拌40小時予以 溶解。在該溶液中加入 AEP之 8.5質量%NMP溶液( 14.8g )(作爲 AEP、1.26g) 、NMP(3.7g) 、:BCS( 5 5.5 g ),在5 0 °C下進行攪拌1 5小時’製得液晶配向處理 劑(7 )。 (實施例8) 藉由在以合成例3所得的聚醯亞胺粉末(C ) ( 7.4g )中加入NMP ( 41.9g ),在70 °C下進行攪拌40小時予以 溶解。在該溶液中加入API之1〇質量%NMP溶液(I2.5g )(作爲 API、1.26g) 、NMP(5.9g) 、BCS(55.5g), 在5 0 °C下進行攪拌1 5小時’製得液晶配向處理劑(8 )。 -67- 200831611 (實施例9 ) 藉由在以合成例4所得的聚醯亞胺粉末(D ) )中加入NMP (57.8g),在70 °C下進行攪拌40小 溶解。在該溶液中加入3-AMP之3質量%NMP 1 0.2g )(作爲 3-AMP、0.31g) 、NMP(6.8g)、 8 5 · 0 g ),在5 0 °C下進行攪拌1 5小時,製得液晶配 劑(9 ) 〇 (實施例1 〇 ) 藉由在以合成例4所得的聚醯亞.胺粉末(D ) )中加入NMP ( 57.8g ),在70°C下進行攪拌40小 溶解。在該溶液中加入3-AMP之5質量%NMP 10.2g )(作爲 3-AMP、0.51g) 、NMP(6.8g)、 85.0g),在50°C下進行攪拌15小時,製得液晶配 劑(10)。 (實施例11 ) 藉由在以合成例4所得的聚醯亞胺粉末(D ) )中加入NMP ( 57.8g ),在70°C下進行攪拌40小 溶解。在該溶液中加入 3-AMP之 7質量%NMP 1 〇 . 2 g )(作爲 3 - A Μ P、0.7 1 g ) 、N Μ P ( 6 · 8 g )、 85.0g),在50°C下進行攪拌15小時,製得液晶配 劑(1 1 )。 (10.2g 時予以 溶液( BCS ( 向處理 (10.2g 時予以 溶液( BCS ( 向處理 (10.2g 時予以 溶液( BCS ( 向處理 -68- 200831611 (實施例1 2 ) 藉由在以合成例4所得的聚醯亞胺粉末(D ) )中加入NMP ( 57.8g ),在70°C下進行攪拌40小 溶解。在該溶液中加入3-AMP之10質量%NMP 10.2g )(作爲 3-AMP、l.〇g) 、NMP(6.8g)、 8 5.0 g ),在5 0 °C下進行攪拌1 5小時,製得液晶配 劑(12)。 (實施例1 3 ) 藉由在以合成例5所得的聚醯亞胺粉末(E ) )中加入NMP(42.0g),在70 °C下進行攪拌40小 溶解。在該溶液中加入3 - A Μ P之7質量% Ν Μ P溶液 )(作爲 3-AMP、0.6g) 、NMP ( 2.4g) 、:BCS (' ,在5 0 °C下進行攪拌1 5小時’製得液晶配向處理 (實施例1 4 ) 藉由在以合成例5所得的聚醯亞胺粉末(E ) )中加入NMP ( 42.0g),在70°C下進行攪拌40小 溶解。在該溶液中加入3-AMP之10質量%NMP 8.6g )(作爲 3-AMP、0.86g) > NMP ( 2.4g )、 7 1 · 7 g ),在5 0 °C下進行攪拌1 5小時’製得液晶配 劑(14)。 (10.2g 時予以 溶液( BCS ( 向處理 (8.6g 時予以 (8.6g r1.7g) 劑(13 (8.6g 時予以 溶液( BCS ( 向處理 -69-LiBr-H20) is 30 mmol/L, phosphoric acid anhydrous crystals (〇_phosphoric acid) is 30 mmol/L, and tetrahydrofuran (THF) is 10 ml/L) as an additive) Flow rate: 1.0 mL/min. : TSK standard polyethylene oxide (molecular weight about 9,000, 150,000, 100,000, 3 〇〇〇〇) manufactured by Dongsuo Co., Ltd., and polymer Labrador (trans) company, the amount of polyethylene glycol is about 12,000, 4,000 , 1,000). <Measurement of ruthenium iodide> The ruthenium imidization ratio of polyimine in the synthesis example was as follows. 2 Omg of polyimine powder was added to an NMR sample tube (NMR by Kusano Scientific Co., Ltd.) The sample tube starter φ 5 ), 0.53 ml of dimethyl hydrazine dihydrogen hydride (DMSO-d5, 0.05% TMS mixture) was added, and ultrasonic waves were applied to completely dissolve the solution. The solution was made by the Japanese electronic Ditham Company. The NMR measuring device (INW-ECA500) was used to measure the proton NMR at 500 MHz. The azylation rate of the yttrium Φ was determined by using protons from a structure that did not change before and after the imidization as a reference proton, and the peaks of the protons were used. The proton peak enthalpy of the NH group of the amino acid present in the vicinity of 9.5 to 10.Oppm is obtained by the following formula: 醯 imidization ratio (%) = ( · x / y ) X 1 00 In the above formula, x is the proton peak cumulative enthalpy derived from the NH group of the amino acid, y is the peak cumulative enthalpy from the reference proton, and α is the i-58-200831611 polyamino acid (醯imination) The ratio of the number of the reference protons in the proton of the NH group of the amino acid at the rate of 〇%). The method for determining the amount was determined by the method described above. (Synthesis Example 1) BODA (16.9 g, 68 mmol), p-PDA (6.8 g, 6 3 mm ο 1 ), PCH (10.3 g, 27 mmol) was mixed in NMP (100.g), and after reacting at 40 ° C for 3 hours, c BDA ( 4 · 1 g, 2 1 mm o 1 ) and NMP ( 5 2.2 g ) were added at 40°. The reaction was carried out for 3 hours at C to obtain a polyaminic acid solution. NMP was added to the polyamic acid solution (1 3 0.3 g), diluted to 6 mass%, and acetic anhydride (1 5 · 6 g ) was added. Pyridine (1 2 · 1 g ) was used as a ruthenium catalyst to carry out a reaction at 80 ° C for 3 hours. The reaction solution was poured into methanol (1 600 ml), and the resulting precipitate was filtered. The mixture was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A). The polyamidimide had a ruthenium imidation ratio of 54%, a number average molecular weight of 18,300, and a weight average molecular weight. It is 45,300. The amount of the carboxyl group of the polyimine is 0.92 for the repeating unit. (Synthesis Example 2) BODA (16.9 g, 68 mmol), p-PDA (6.8 g, 63 mmol), PCH (10. 3 g, 2 7 mmol ) in NMP ( 100 0g) mixed, after fT reaction at 40 ° C for 3 hours, 'CBDA (4.1g, 21mmol -59-200831611) and NMP (52.2g) were added, and the reaction was carried out at 40 °C for 3 hours to obtain polyfluorene. Amino acid solution. NMP was added to the polyamic acid solution (55.4 g), and after diluting to 6 mass%, acetic anhydride (2.7 g) and pyridine (2.1 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 70 ° C. 1 hour. The reaction solution was poured into methanol (660 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimide powder (B). The polyimine had a hydrazine imidization ratio of 25%, a number average molecular weight of 19,500, and a weight average molecular weight of 47,800. The amount of the carboxyl group of the polyimine was 1.50 for the repeating unit. (Synthesis Example 3) BODA (1 50.1 g, 600 mmol), DBA (60.9 g, 400 mmol), PCH (152.2 g, 400 mmol) were mixed in NMP (1290 g), and the reaction was carried out at 80 ° C for 5 hours, and then added. CBDA (38.8 g, 198 mmol) and NMP (3 20 g) were reacted at 40 ° C for 3 hours to prepare a polyaminic acid solution. Into the polyaminic acid solution (600.2 g), Ν Μ P was added, and after diluting to 6% by mass, acetic acid drunk (6 3 · 9 g ) and pyridin (49.6 g) were added as a ruthenium amide catalyst. The reaction was carried out at 80 ° C for 3 hours. The reaction solution was poured into methanol (7700 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (C). The polyimine had a ruthenium iodide ratio of 57%, a number average molecular weight of 23,000, and a weight average molecular weight of 80,200. The amount of the carboxyl group of the polyimine is 1.36 for the repeating unit. -60 - 200831611 (Synthesis Example 4) BODA (50.1 g, 600 mmol), DBA (60.9 g, 400 mmol), PCH (152.2 g, 400 mmol) were mixed in NMP (1 290 g), and the reaction was carried out at 80 °C. After the hour, CBDA (38.8 g, 198 mmol) and NMP (320 g) were added, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (30O.lg) and diluting it to 6 mass%, acetic anhydride (32.0 g) and pyridine φ (24.8 g) were added as a ruthenium catalyzed catalyst at 90 ° C. The reaction was carried out for 2.5 hours. The reaction solution was poured into methanol (3900 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (D). The polyimine had a hydrazine imidation ratio of 69%, a number average molecular weight of 22,700, and a weight average molecular weight of 69,300. The amount of the carboxyl group of the polyimine was 1.12 for the repeating unit. (Synthesis Example 5) BODA (150.lg '600 mmol), DBA (60.9 g, 400 mmol), and PCH (152.2 g, 40 mmol) were mixed in NMP (1 2 9 0 g), and the mixture was carried out at 80 ° C. After reacting for 5 hours, CBDA (3 8.8 g, 1 98 mmol) and NMP (3 20 g) were added, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (101.2 g) and diluting it to 6 mass%, acetic anhydride (21.3 g) and pyridine (16.5 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 90 ° C. 3 hours. The reaction solution was poured into methanol (1 300 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C. -61 - 200831611 to obtain a polyimine powder (E). The polyimine had an oxime imidization ratio of 81%, a number average molecular weight of 20,400, and a weight average molecular weight of 63. The amount of the carboxyl group of the polyimine is 〇.88 for the repeating unit. (Synthesis Example 6) BODA (16.0 g, 64 mmol), DAD PA (H*9 g 60 mmol), PCH (9.7 g, 26 mmol) were mixed in NMP (126.4 g), and the reaction was carried out at 40 ° C for 3 hours. Thereafter, CBDA (3.8 g, 19 mmol) and NMP (40 g) were added, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. NMP was added to the polyamic acid solution (5 〇. 3 g), and after diluting to 4% by mass, acetic anhydride (5.0 g) and pyridin (3.9 g) were added as a ruthenium catalyst, at 50 The reaction was carried out at ° C for 2 hours. The reaction solution was poured into methanol (91 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 1 ° C to obtain a polyimine powder (F). The polyamidimide had a ruthenium iodide ratio of 25% φ, a number average molecular weight of 22,200, and a weight average molecular weight of 69,000. The amount of the carboxyl group of the polyimine was 1.50 for the repeating unit. (Synthesis Example 7) BODA (7.5 g, 30 mmol), DADPA (1.6 g, 8.0 mm ο 1 ), DBA (2.4 g, 16 mmol), PCH (6.1 g, 16 mmol) in NMP (5 3.2 g ) After mixing and reacting at 40 ° C for 3 hours, CBDA (1.9 g, 10 mmol) and NMP (25 g) were vigorously introduced, and the reaction was carried out at 40 ° C for 3 hours to obtain a polyaminic acid solution. Add NMP to the polyamine-62 - 200831611 amino acid solution (60.4g), dilute to 5% by mass, add acetic anhydride (6 · 3 g ), pyridine (4 · 9 g ) as ruthenium amide catalyst The reaction was carried out at 90 ° C for 2 hours. The reaction solution was poured into methanol (8 80 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (〇). The polyimine had a hydrazine imidation ratio of 51%, a number average molecular weight of 21,100, and a weight average molecular weight of 64,000. The amount of the carboxyl group of the polyimine was 1.38 for the repeating unit. (Synthesis Example 8) TDA (9.0 g, 30 mmol), DBA (3.2 g, 21 mmo 1 ), p-PDA (1.0 g, 9.0 mmol) were mixed in NMP (74.7 g), and the reaction was carried out at room temperature. In hours, a polyaminic acid solution was prepared. After adding NMP to the polyamic acid solution (80.0 g) and diluting it to 6% by mass, acetic anhydride (2 9 · 1 g ) and pyridine (1 3 · 5 g ) were added as a ruthenium-based catalyst. The reaction was carried out at 3 ° C for 3 hours. The reaction solution was poured into methanol (7 μm ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (Η). The polyamidimide had a ruthenium imidation ratio of 91%, a number average molecular weight of ιυοο, and a weight average molecular weight of 20,570. The amount of the carboxyl group of the polyimine was 0.88 for the repeating unit. (Example 1) NMP (41.9 g) was added to the polyimine powder (a) (7.4 g - 63 - 200831611) obtained in Synthesis Example 1, and stirred at 80 ° C for 40 minutes to dissolve. To the solution, 7.5 14.8 g of 3_AMP (as 3-AMP, 1.1 L), NMP (3.7 g), 55.5 g) was added, and the mixture was stirred at 50 ° C for 15 hours to prepare a liquid crystal formulation (1). . <Production of Liquid Crystal Cell> The liquid crystal alignment treatment agent (1) obtained above was spin-coated on a glass substrate coated with an ITO electrode, and dried on a hot plate at 80 ° C to obtain a hot air of 2 10 ° C. A liquid crystal alignment film having a film thickness of 100 nm was fired in a circulating oven for 1 hour. Two sheets of the liquid crystal alignment plate were used, and a sealant was printed on a liquid crystal alignment film of one of them, and the sealant was printed thereon, and the sealant was hardened to produce a cell. In the empty cell, a liquid crystal ML C-Meru Valley (manufactured by Nippon Co., Ltd.) was injected by a vacuum injection method to seal the injection port and the liquid crystal cell. When the liquid crystal cell was observed under a polarizing microscope, the liquid crystal was uniformly aligned, and there was no alignment defect. <Evaluation of voltage holding ratio> The voltage of the liquid crystal cell produced above was measured at a temperature of 80 ° C, a voltage of 4 V, 60 μδ, and after 16.67 ms and after 166 7 ms, the voltage was maintained as a voltage holding ratio. As a result, the retention rate of 16.67 ms was 97.6%, and the voltage retention rate of 1 667 ms was 67.3%. At the time of the solution (BCS (to the treatment for 5 minutes, after making the base of the film, for the air crystal 6608 (the pressure is applied to the ground vertically, the voltage is -64-200831611 and the measurement system uses the Toyo Digu The VHR-1 voltage retention rate measuring device manufactured by Nika Corporation is measured at a setting of Voltage: ±4V, Pulse Width: 60ps, Flame Period: 16.67ms or 1667ms. <Evaluation of Residual Charge Mitigation> A voltage of 10 V for 30 minutes was applied to the liquid crystal cell after the voltage holding ratio measurement, and a short circuit occurred for 1 second, and then a potential generated in the liquid crystal cell was measured for 1 800 seconds. The potential change at this time is as shown in Fig. 1. As a result, the residual charge after 50 seconds after the short circuit was 3.19 V, and the residual charge after 1 000 seconds was 0.25 V. Further, the measurement was performed using a 6254 liquid crystal physical property evaluation device manufactured by Toyo Digunik Co., Ltd. Evaluation after high-temperature placement> The liquid crystal cell which was subjected to the above measurement was placed in a thermostat set at 100 ° C for 7 days, and the same measurement was performed. As a result, the voltage retention rate of 16.67 ms was 97.8%, 1 66 The voltage retention rate of 7 ms was 67.2%, the residual charge after 50 seconds was 3.41 V, and the residual charge after 1 000 seconds was 0.46 V. (Example 2 to Example 1 8) The liquid crystal alignment treatment agent was prepared as follows (2) ~(1 8 ), a liquid crystal cell was produced and evaluated in the same manner as in Example 1. In all of the unit cells, the liquid crystal was uniformly aligned vertically, and there was no alignment defect. The evaluation results are shown in Tables 1 and 2 below. -65-200831611 (Example 2) A liquid crystal alignment treatment agent (2) was prepared in the same manner as in Example 1 except that the polyimine powder (B) obtained in Synthesis Example 2 was used. The liquid crystal alignment treatment agent (3) was prepared in the same manner as in Example 1 except that the polyimine powder (C) obtained in Synthesis Example 3 was dissolved by stirring at 7 ° C for 40 hours. (Example 4) NMP (30.6 g) was added to the polyimine powder (C) (5.4 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 40 hours to dissolve. Add 3-AMP 1% by mass NMP solution (5.4g) (as 3-AMP, 0.38g), NMP (8.1g), BCS (4 0.5g), at 50 The liquid crystal alignment treatment agent (4) was obtained by stirring at ° C for 15 hours. (Example 5) By adding NMP (30.6 g) to the polyimine powder (C) (5.4 g) obtained in Synthesis Example 3. The mixture was stirred at 70 Torr for 40 hours to dissolve. To this solution, a 7 mass% hydrazine solution (5.4 g) (as 3-AMP, 〇.38 g), NMP (8.1 g), BCS (40.5 g) was added to the solution, and the mixture was stirred at 50 ° C. In the hour, a liquid crystal alignment treatment agent was prepared (5-66-200831611 (Example 6). By adding NMP (41.9 g) to the polyimine powder (C) (7.4 g) obtained in Synthesis Example 3, at 70 The mixture was stirred for 40 hours at ° C to dissolve. A solution of 5-AMP in NMP (7.4 g) (as 3-AMP, 0.37 g), NMP (ll.lg), BCS (55.5 g) was added to the solution. The mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (6 (Example 7) by adding NMP to the polyimine powder (C) (7.4 g) obtained in Synthesis Example 3. (41.9 g) was dissolved by stirring at 70 ° C for 40 hours. A solution of 8.5% by mass of NEP (14.8 g) (as AEP, 1.26 g), NMP (3.7 g), and BCS (ACS) was added to the solution. 5 5.5 g ), stirring at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (7 ). (Example 8) By using the polyimide pigment (C) obtained in Synthesis Example 3 ( Add NMP (41.9g) to 7.4g) and stir at 70 °C It was dissolved in 40 hours. To the solution was added API 1% by mass NMP solution (I2.5g) (as API, 1.26g), NMP (5.9g), BCS (55.5g), at 50 °C. The liquid crystal alignment treatment agent (8) was prepared by stirring for 15 hours. -67-200831611 (Example 9) By adding NMP (57.8 g) to the polyimine powder (D) obtained in Synthesis Example 4, Stirring was carried out at 70 ° C for 40 minutes. To the solution was added 3-AMP 3 mass % NMP 1 0.2 g ) (as 3-AMP, 0.31 g), NMP (6.8 g), 8 5 · 0 g ) The mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal formulation (9 ) 〇 (Example 1 〇) by adding NMP to the polyamidamine powder (D) obtained in Synthesis Example 4. (57.8 g), stirred at 70 ° C for 40 minutes to dissolve. To the solution, 5-AMP-5 mass% NMP (10 g) (as 3-AMP, 0.51 g), NMP (6.8 g), and 85.0 g) was added, and the mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal. Agent (10). (Example 11) NMP (57.8 g) was added to the polyimine powder (D) obtained in Synthesis Example 4, and stirred at 70 ° C for 40 minutes to dissolve. To this solution, 7 mass% of NAMP 1 〇. 2 g ) (as 3 - A Μ P, 0.7 1 g ), N Μ P (6 · 8 g ), 85.0 g) was added at 50 ° C. The mixture was stirred for 15 hours to obtain a liquid crystal formulation (1 1 ). (10.2 g of the solution (BCS) (to the treatment (10.2 g of the solution (BCS (to the treatment (10.2 g of the solution (BCS (to the treatment -68-200831611 (Example 1 2) by using Synthesis Example 4 To the obtained polyimine powder (D)), NMP (57.8 g) was added, and stirring was carried out at 70 ° C for 40 minutes. To the solution, 10 mass % of NAMP (10 mass %) was added to the solution (as a 3- AMP, l. g), NMP (6.8 g), 8 5.0 g), stirring at 50 ° C for 15 hours to obtain a liquid crystal formulation (12). (Example 1 3 ) NMP (42.0 g) was added to the polyimine powder (E) obtained in Synthesis Example 5, and stirred at 70 ° C for 40 minutes to dissolve. 7 % by mass of 3 - A Μ P was added to the solution Ν Μ P Solution) (as 3-AMP, 0.6g), NMP (2.4g), :BCS (', stirring at 50 ° C for 15 hours to obtain liquid crystal alignment treatment (Example 14)) NMP (42.0 g) was added to the polyimine powder (E) obtained in Synthesis Example 5, and stirred at 70 ° C for 40 minutes to dissolve. To the solution, 10 mass % of NMP (8.6 g of 3-AMP) was added ( As 3-AMP, 0.86g) > NMP (2.4g), 7 1 · 7 g ) The liquid crystal formulation (14) was prepared by stirring at 50 ° C for 15 hours. (A solution was prepared at 10.2 g (BCS) (treated to 8.6 g (8.6 g r1.7 g) (13 g (8.6 g) Time to solution (BCS (to treatment -69-
200831611 (實施例1 5 ) 藉由在以合成例6所得的聚醯亞胺粉末(F ) )中加入NMP (41.9g),在80。(:下進行攪拌40小 溶解。在該溶液中加入3-AMP之10質量°/^1^ 1 1 . 1 g )(作爲 3-AMP、l.llg) 、NMP(7.4g)、 55.5g),在50°C下進行攪拌15小時,製得液晶配 劑(1 5 ) 〇 (實施例1 6 ) 藉由在以合成例7所得的聚醯亞胺粉末(G )200831611 (Example 1 5) NMP (41.9 g) was added at 80 by the polyimine powder (F) obtained in Synthesis Example 6. (: 40 times of stirring under stirring. Add 10 mass of 3-AMP to /1 1 ^ 1 1 .1 g ) (as 3-AMP, l.llg), NMP (7.4g), 55.5g The mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal formulation (15) 〇 (Example 16) by using the polyimine powder (G) obtained in Synthesis Example 7.
)中加入NMP ( 41.9g ),在80°C下進行攪拌40小 溶解。在該溶液中加入3-AMP之5質量%NMP溶液 )(作爲 3-AMP、0.37g) ' NMP ( 11.lg) 、:BCS ),在5 0 °C下進行攪拌1 5小時,製得液晶配向處 (7.4g 時予以 溶液( BCS ( 向處理 (7.4g 時予以 (7.4g (55.5g 理劑(NMP (41.9 g) was added thereto, and the mixture was stirred at 80 ° C for 40 minutes to dissolve. To this solution, 3-AMP 5 mass% NMP solution (as 3-AMP, 0.37 g) 'NMP (11 lg), :BCS) was added, and the mixture was stirred at 50 ° C for 15 hours to obtain a solution. Liquid crystal alignment (solution at 7.4g (BCS (to treatment (7.4g (55.5g (55.5g)
(實施例1 7 ) 藉由在以合成例5所得的聚醯亞胺粉末(E ) )中加入NMP (42.0g),在80 °C下進行攪拌40小 溶解。在該溶液中加入4-AMP之7質量%NMP溶液 )(作爲 4-AMP、〇.6g) 、NMP(2.4g) 、BCS(' ,在50 °C下進行攪拌15小時,製得液晶配向處理 (8-6g 時予以 (8 · 6 g r1.7g) 劑(17 -70 - 200831611 (實施例1 8 ) 藉由在以合成例7所得的聚醯亞胺粉末(E ) ( 8.6g )中加入NMP ( 42.0g),在80°C下進行攪拌40小時予以 溶解。在該溶液中加入2AMMP之7質量%NMP溶液( 8.6g )(作爲 2AMMP、0.6g) 、NMP(2.4g) 、BCS( 71.7g),在50°C下進行攪拌15小時,製得液晶配向處理 劑(1 8 )。 (比較例1 ) 藉由在以合成例1所得的聚醯亞胺粉末(A) ( 7.4g )中加入NMP ( 41.9g),在80°C下進行攪拌40小時予以 溶解。在該溶液中加入NMP (18.5g) 、BCS(55.5g), 進行攪拌1小時,製得液晶配向處理劑(1 9 )。使用該液 晶配向處理劑,與實施例1相同地製作液晶晶胞且予以評 • 估。 使該液晶晶胞以偏光顯微鏡進行觀察時,液晶爲均勻 地垂直配向,沒有配向缺陷情形。 <電壓保持率之評估> 使上述所製作的液晶晶胞與實施例1相同地測定電壓 保持率時,16.6 7ms之電壓保持率爲97.4%’ 1667ms之電 壓保持率爲64.1%。 -71 - 200831611 <殘留電荷緩和之評估> 使測定電壓保持率後之液晶晶胞以與實施例1相同的 方法進行評估殘留電荷緩和之評估時,短路後5 0秒後之 殘留電荷爲2.63V,1 000秒後之殘留電荷爲0.61V。 <高溫放置後之評估> 使上述測定完成的液晶晶胞與實施例1相同的方法, Φ 在設定於1 〇 〇 °C之恆溫槽中放置7日後,進行電壓保持率 及殘留電荷緩和之評估。結果,16.67ms之電壓保持率爲 97.2%,1 667ms之電壓保持率爲57.7%,50秒後之殘留電 荷爲4.33V,1 000秒後之殘留電荷爲2.62V。 (比較例2〜比較例8 ) 如下所述調製液晶配向處理劑(20 )〜(26 ),與實 施例1相同地製作液晶晶胞。 • 於全部液晶晶胞中,液晶均勻地垂直配向,沒有配向 缺陷情形。 使用所製作的液晶晶胞,以與實施例1相同的方法, 進行電壓保持率、殘留電荷之緩和、及高溫放置後之評估 。評估結果如下述表1及表2所記載。 (比較例2 ) 藉由在以合成例3所得的聚醯亞胺粉末(C )( 7.4 g )中加入NMP ( 41.9g),在70°C下進行攪拌40小時予以 -72- 200831611 溶解。在該溶液中加入NMP ( 1 8 · 5 g ) 、B C S ( 5 5 · 5 g ), 進行攪拌1小時,製得液晶配向處理劑(20 )。 (比較例3 ) 除使用Py取代3-AMP,且對聚醯亞胺粉末(C )( 7.4g)而言混合Py ( 0.81g)外,與實施例3相同地製得 液晶配向處理劑(2 1 )。 (比較例4 ) 除使用ΑΡΜΑ取代3 _ amp外,與實施例3相同地製 得液晶配向處理劑(22)。 (比較例5 ) 除使用MI取代3_AMp外,與實施例3相同地製得液 晶配向處理劑(23 )。 參 (比較例6 ) 除使用VPy取代3_AMp外,與實施例3相同地製得 液晶配向處理劑(2 4 )。 (比較例7) 除使用 AP 7.4g)而言混合 液晶配向處理劑 取代3-AMP ’且對聚醯亞胺粉末(c )( AP ( 1.2 6 g )外,與實施例3相同地製得 (25)。 -73- 200831611 (比較例8 ) 除使用HA取代3-AMP外,與實施例3相同地製得液 晶配向處理劑(2 6 )。(Example 1 7) NMP (42.0 g) was added to the polyimine powder (E) obtained in Synthesis Example 5, and stirred at 80 ° C for 40 minutes to dissolve. To this solution, 4-AMP 7 mass% NMP solution (as 4-AMP, 〇.6g), NMP (2.4g), and BCS (' were stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment. Treatment (8-6 g of (8 · 6 g r 1.7 g) agent (17 - 70 - 200831611 (Example 18) by using the polyimine powder (E) obtained in Synthesis Example 7 (8.6 g) NMP (42.0 g) was added thereto, and the mixture was stirred at 80 ° C for 40 hours to dissolve. 2MMP of 7 mass% NMP solution (8.6 g) (as 2AMMP, 0.6 g) and NMP (2.4 g) were added to the solution. BCS (71.7 g) was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (1 8 ). (Comparative Example 1) By the polyimine powder (A) obtained in Synthesis Example 1 ( NMP (41.9 g) was added to 7.4 g of the solution, and the mixture was stirred at 80 ° C for 40 hours to dissolve. NMP (18.5 g) and BCS (55.5 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment. Using the liquid crystal alignment treatment agent, a liquid crystal cell was produced and evaluated in the same manner as in Example 1. When the liquid crystal cell was observed with a polarizing microscope, the liquid crystal was uniformly aligned vertically, and In the case of the alignment defect, <Evaluation of voltage holding ratio> When the voltage holding ratio was measured in the same manner as in Example 1 in the liquid crystal cell produced as described above, the voltage holding ratio of 16.6 ms was 97.4%', and the voltage holding ratio of 1667 ms was 64.1. -71 - 200831611 <Evaluation of Residual Charge Relaxation> The liquid crystal cell after the measurement of the voltage holding ratio was evaluated in the same manner as in Example 1 to evaluate the residual charge relaxation, and the residue after 50 seconds after the short circuit The electric charge was 2.63 V, and the residual electric charge after 1 000 seconds was 0.61 V. <Evaluation after high temperature standing> The liquid crystal cell having the above measurement was completed in the same manner as in Example 1, Φ was set at 1 〇〇 ° C After 7 days in the constant temperature bath, the voltage holding ratio and the residual charge relaxation were evaluated. As a result, the voltage retention of 16.67 ms was 97.2%, the voltage retention of 1 667 ms was 57.7%, and the residual charge after 50 seconds was 4.33 V. The residual charge after 1.000 seconds was 2.62 V. (Comparative Example 2 to Comparative Example 8) Liquid crystal alignment treatment agents (20) to (26) were prepared as described below, and a liquid crystal cell was produced in the same manner as in Example 1. All liquid crystal cells Uniformly vertically aligned liquid crystal, no alignment defect situation using a liquid crystal cell produced in the same method as in Example 1, a voltage holding ratio, relaxation of the residual charge, and the evaluation of high-temperature place. The evaluation results are as shown in Tables 1 and 2 below. (Comparative Example 2) NMP (41.9 g) was added to the polyimine powder (C) (7.4 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 40 hours to be dissolved in -72 - 200831611. NMP (1 8 · 5 g ) and B C S (5 5 · 5 g) were added to the solution, and the mixture was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (20). (Comparative Example 3) A liquid crystal alignment treatment agent was prepared in the same manner as in Example 3 except that Py was used instead of 3-AMP, and Py (0.81 g) was mixed with the polyimine powder (C) (7.4 g). twenty one ). (Comparative Example 4) A liquid crystal alignment treatment agent (22) was obtained in the same manner as in Example 3 except that hydrazine was used instead of 3 amp. (Comparative Example 5) A liquid crystal alignment treatment agent (23) was obtained in the same manner as in Example 3 except that MI was used instead of 3_AMp. (Comparative Example 6) A liquid crystal alignment treatment agent (2 4 ) was obtained in the same manner as in Example 3 except that VPy was used instead of 3_AMp. (Comparative Example 7) The same procedure as in Example 3 was carried out except that the mixed liquid crystal alignment agent was replaced with 3-AMP' using AP 7.4 g) and the polyimine powder (c) (AP (1.2 6 g ) was used. (25) -73-200831611 (Comparative Example 8) A liquid crystal alignment treatment agent (2 6 ) was obtained in the same manner as in Example 3 except that HA was used instead of 3-AMP.
聚醯亞胺 胺化合物 電壓保持率(%) 液晶晶 室製作時 高溫放置後 16.67ms 1667ms 16.67ms 1667ms 實施例1 A 3-AMP 97.6 67.3 97.8 67.2 實施例2 B 3-AMP 97.0 53.0 96.7 52.0 實施例3 C 3-AMP 97.8 63,5 97.7 63.6 實施例4 C 3-AMP 97.8 64.6 97.9 64.3 實施例5 C 3-AMP 97.8 64.1 97.9 65.0 實施例6 C 3-AMP 97.8 64.8 97.8 60.9 實施例7 C AEP 97.5 61.0 97.4 62.7 實施例8 C API 97.3 62.5 97.3 68.6 實施例9 D 3-AMP 98.1 68.3 98.0 68.2 實施例10 D 3-AMP 98.1 68.2 98,1 68.1 實施例11 D 3-AMP 98.0 68.0 98.0 68.1 實施例12 D 3-AMP 98.1 68.0 98.1 68.0 實施例Π E 3-AMP 98.0 68.2 98.1 68.3 實施例14 E 3-AMP 97.8 67.8 98.0 67.8 實施例15 F 3-AMP 97.5 54.1 97.7 56.3 實施例16 G 3-AMP 97.8 67.8 98.1 67.8 實施例17 E 4-AMP 98.1 68.6 98.2 68.5 實施例18 E 2AMMP 98.1 67.2 98.0 67.4 比較例1 A - 97.4 64.1 97.2 57.7 比較例2 C - 97.8 62.6 97.6 63.1 比較例3 C Py 97.8 63.6 97.6 62.3 比較例4 c ΑΡΜΑ 96.6 31.5 96.7 31.6 比較例5 c MI 96.9 50.5 96.8 48.9 比較例6 c VPy 97.6 64.0 97.7 64.0 比較例7 c AP 97.6 62.4 97.5 62.6 比較例8 c HA 97.3 64.2 97.2 64.0 -74- 200831611Polyimine amine compound voltage retention rate (%) 16.67 ms 1667 ms 16.67 ms 1667 ms after high temperature placement in liquid crystal cell preparation Example 1 A 3-AMP 97.6 67.3 97.8 67.2 Example 2 B 3-AMP 97.0 53.0 96.7 52.0 Example 3 C 3-AMP 97.8 63,5 97.7 63.6 Example 4 C 3-AMP 97.8 64.6 97.9 64.3 Example 5 C 3-AMP 97.8 64.1 97.9 65.0 Example 6 C 3-AMP 97.8 64.8 97.8 60.9 Example 7 C AEP 97.5 61.0 97.4 62.7 Example 8 C API 97.3 62.5 97.3 68.6 Example 9 D 3-AMP 98.1 68.3 98.0 68.2 Example 10 D 3-AMP 98.1 68.2 98, 1 68.1 Example 11 D 3-AMP 98.0 68.0 98.0 68.1 Example 12 D 3-AMP 98.1 68.0 98.1 68.0 Example Π E 3-AMP 98.0 68.2 98.1 68.3 Example 14 E 3-AMP 97.8 67.8 98.0 67.8 Example 15 F 3-AMP 97.5 54.1 97.7 56.3 Example 16 G 3-AMP 97.8 67.8 98.1 67.8 Example 17 E 4-AMP 98.1 68.6 98.2 68.5 Example 18 E 2AMMP 98.1 67.2 98.0 67.4 Comparative Example 1 A - 97.4 64.1 97.2 57.7 Comparative Example 2 C - 97.8 62.6 97.6 63.1 Comparative Example 3 C Py 97.8 63.6 97.6 62.3 Comparison Example 4 c ΑΡΜΑ 96.6 31.5 96.7 31.6 Comparative Example 5 c MI 96.9 50.5 96.8 48.9 Comparative Example 6 c VPy 97.6 64.0 97.7 64.0 Comparative Example 7 c AP 97.6 62.4 97.5 62.6 Comparative Example 8 c HA 97.3 64.2 97.2 64.0 -74- 200831611
表2 聚醯亞胺 胺化合物 殘留電荷之緩和(V) 液晶晶月 1 妄製作時 高溫放置後 50秒後 1000秒後 50秒後 1000秒後 實施例1 A 3-AMP 3.19 0.25 3.41 0.46 實施例2 B 3-AMP 2.96 0.17 1.47 0.19 實施例3 C 3-AMP 2.61 0.25 1.28 0.30 實施例4 C 3-AMP 1.54 0.15 1.39 0.24 實施例5 C 3-AMP 2.94 0.17 2.21 0.48 實施例6 C 3-AMP 3.05 0.17 2.01 0.41 實施例7 C AEP 1.47 0.14 1.13 0.23 實施例8 C API 2.99 0.17 1.26 0.28 實施例9 D 3-AMP 3.04 0.34 2.76 1.13 實施例10 D 3-AMP 3.02 0.25 2.29 0.64 實施例11 D 3-AMP 2.77 0.20 2.75 0.62 實施例12 D 3-AMP 2.87 0.25 2.54 0.59 實施例13 E 3-AMP 3.26 0.22 3.34 1.15 實施例14 E 3-AMP 3.18 0.30 2.84 0.80 實施例15 F 3-AMP 1.94 0.18 1.62 0.34 實施例16 G 3-AMP 2.29 0.16 2.38 0.58 實施例17 E 4-AMP 3.21 0.26 3.19 1.07 實施例18 E 2AMMP 3.15 0.28 3.17 0.97 比較例1 A - 2.63 0.61 4.33 2.62 比較例2 C - 2.21 0.66 3.68 1.88 比較例3 C Py 2.18 0.67 3.72 1.74 比較例4 C ΑΡΜΑ 2.60 0.73 3.90 2.36 比較例5 C MI 2.83 0.65 3.83 1.85 比較例6 C VPy 3.07 0.60 3.72 2.12 比較例7 C AP 2.64 0.55 3.64 2.42 比較例8 C HA 2.97 0.68 3.91 2.38 〔產業上之利用價値〕 本發明之液晶配向處理劑,電壓保持率高,且在高溫 -75- 200831611 下長時間暴露後仍可得藉由直流電壓所囤積的殘留電荷之 緩和快速的液晶配向膜。因此,藉此所得的液晶顯示元件 ’即使長時間使用,可抑制畫面燒付或顯示斑之顯示不良 情形,爲信賴性優異者,可適合利用於大畫面、高精細的 液晶電視等。而且,該液晶顯示元件可適合使用於各種顯 示裝置。 此外,此處引用2006年7月28日提出申請的日本專 利申請2〇06_2 0661 7號之說明書、申請專利範圍、圖面及 摘要說明之全部內容,作爲本說明說明書之揭示所採用者 【圖式簡單說明】 〔第1圖〕係表示於實施例1中進行殘留電荷之緩和 評估時的電位變化圖。 -76-Table 2 Relaxation of Residual Charge of Polyimine Amine Compound (V) Liquid Crystal Crystal 1 妄 After preparation of high temperature after 50 seconds, after 1000 seconds, after 50 seconds, and after 1000 seconds, Example 1 A 3-AMP 3.19 0.25 3.41 0.46 Example 2 B 3-AMP 2.96 0.17 1.47 0.19 Example 3 C 3-AMP 2.61 0.25 1.28 0.30 Example 4 C 3-AMP 1.54 0.15 1.39 0.24 Example 5 C 3-AMP 2.94 0.17 2.21 0.48 Example 6 C 3-AMP 3.05 0.17 2.01 0.41 Example 7 C AEP 1.47 0.14 1.13 0.23 Example 8 C API 2.99 0.17 1.26 0.28 Example 9 D 3-AMP 3.04 0.34 2.76 1.13 Example 10 D 3-AMP 3.02 0.25 2.29 0.64 Example 11 D 3-AMP 2.77 0.20 2.75 0.62 Example 12 D 3-AMP 2.87 0.25 2.54 0.59 Example 13 E 3-AMP 3.26 0.22 3.34 1.15 Example 14 E 3-AMP 3.18 0.30 2.84 0.80 Example 15 F 3-AMP 1.94 0.18 1.62 0.34 Example 16 G 3-AMP 2.29 0.16 2.38 0.58 Example 17 E 4-AMP 3.21 0.26 3.19 1.07 Example 18 E 2AMMP 3.15 0.28 3.17 0.97 Comparative Example 1 A - 2.63 0.61 4.33 2.62 Comparative Example 2 C - 2.21 0.66 3.68 1.88 Comparative Example 3 C Py 2.18 0.67 3.72 1.74 Comparative Example 4 C ΑΡ Α 2.60 0.73 3.90 2.36 Comparative Example 5 C MI 2.83 0.65 3.83 1.85 Comparative Example 6 C VPy 3.07 0.60 3.72 2.12 Comparative Example 7 C AP 2.64 0.55 3.64 2.42 Comparative Example 8 C HA 2.97 0.68 3.91 2.38 [Industrial Utilization Price] The present invention The liquid crystal alignment agent has a high voltage holding ratio, and after a long time exposure at a high temperature of -75 to 200831611, a liquid crystal alignment film which relaxes the residual charge by the DC voltage can be obtained. Therefore, the liquid crystal display element ’ thus obtained can suppress the display failure of the screen burnt or the display spot even if it is used for a long period of time, and can be suitably used for a large-screen, high-definition liquid crystal television or the like for excellent reliability. Moreover, the liquid crystal display element can be suitably used for various display devices. In addition, the entire contents of the specification, the scope of the application, the drawings and the abstract description of the Japanese Patent Application No. 2 〇 06_2 0661, filed on Jul. 28, 2006, which is incorporated herein by reference. Brief Description of the Drawings [Fig. 1] shows a potential change diagram when the relaxation of residual charge is evaluated in the first embodiment. -76-
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WO2018070398A1 (en) * | 2016-10-12 | 2018-04-19 | コニカミノルタ株式会社 | Transparent polyimide resin, transparent polyimide resin composition, transparent polyimide resin film, infrared absorbing composition, infrared cut filter, and production method for transparent polyimide resin film |
JP7100297B2 (en) * | 2017-03-30 | 2022-07-13 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
KR102030079B1 (en) | 2017-06-30 | 2019-10-08 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
CN115244105A (en) * | 2020-03-13 | 2022-10-25 | 日产化学株式会社 | Polyimide varnish |
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JPH01242631A (en) * | 1988-03-24 | 1989-09-27 | Japan Synthetic Rubber Co Ltd | Production of polyimide precursor film |
JP3425343B2 (en) * | 1996-10-31 | 2003-07-14 | 株式会社東芝 | Positive photosensitive polymer resin composition, pattern forming method using the same, and electronic component |
JPH10212484A (en) * | 1997-01-30 | 1998-08-11 | Jsr Corp | Liquid crystal aligning agent |
JP4045595B2 (en) * | 2003-04-22 | 2008-02-13 | Jsr株式会社 | Liquid crystal alignment agent |
-
2007
- 2007-07-27 TW TW096127599A patent/TWI437045B/en active
- 2007-07-27 CN CN2007800285377A patent/CN101495915B/en active Active
- 2007-07-27 WO PCT/JP2007/064814 patent/WO2008013285A1/en active Application Filing
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Cited By (3)
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TWI650349B (en) * | 2012-11-16 | 2019-02-11 | 日商日產化學工業股份有限公司 | Polyimide resin film and electronic device substrate comprising polyimide resin film |
TWI714066B (en) * | 2018-05-17 | 2020-12-21 | 南韓商Lg化學股份有限公司 | Liquid crystal alignment agent composition, method of preparing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display using the same |
US11149204B2 (en) | 2018-05-17 | 2021-10-19 | Lg Chem, Ltd. | Liquid crystal alignment agent composition, method for preparing liquid crystal alignment film using same, and liquid crystal alignment film and liquid crystal display using same |
Also Published As
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JPWO2008013285A1 (en) | 2009-12-17 |
CN101495915A (en) | 2009-07-29 |
WO2008013285A1 (en) | 2008-01-31 |
CN101495915B (en) | 2010-12-15 |
KR101426102B1 (en) | 2014-08-05 |
KR20090052317A (en) | 2009-05-25 |
JP5003682B2 (en) | 2012-08-15 |
TWI437045B (en) | 2014-05-11 |
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