TW201202176A - Diamine compound, liquid crystal aligning agent and liquid crystal display element - Google Patents
Diamine compound, liquid crystal aligning agent and liquid crystal display element Download PDFInfo
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- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- 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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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- 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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- 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
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Abstract
Description
201202176 六、發明說明： 【發明所屬之技術領域】 本發明係關於可使用作爲於液晶配向膜等使用之聚合 物的原料之新穎二胺化合物、使用其所得之聚醯胺酸及聚 醯亞胺以及液晶配向劑。再者，有關具有由前述液晶配向 劑所得之液晶配向膜之液晶顯示元件。 【先前技術】 目前作爲液晶顯示元件之液晶配向膜主要係使用將聚 醯胺酸等之聚醯亞胺前驅物或可溶性聚醯亞胺作爲主成分 之液晶配向劑進行塗佈並燒成爲塗膜，接著使該塗膜進行 摩擦處理所得之液晶配向膜》該摩擦處理由於係以布摩擦 塗膜表面而進行，因此有對液晶配向膜帶來削減傷痕的問 題，但液晶顯示元件之一部分用途有以更強條件進行摩擦 處理之傾向。其目的係藉由進行強的摩擦處理而使液晶配 相狀態更均一且成爲更強固者。因此，關於液晶配向膜之 摩擦耐性之要求變高。 獲得藉由摩擦處理難以引起膜之削減或傷痕之液晶配 向膜之方法，已知有於聚醯亞胺或聚醯亞胺前驅物中添加 各種添加劑之方法（例如參考專利文獻1及專利文獻2 ) » 除此以外，亦提案有摩擦耐性良好之聚醯亞胺構造（例如 參考專利文獻3及專利文獻4)。 且，液晶顯示元件爲了利用電壓驅動液晶，亦對液晶 配向膜要求電特性。因此，對液晶配向膜所要求之代表性 -5- 201202176 電特性之一爲電壓保持率。所謂電壓保持率，係表示對液 晶胞施加之電壓經過一定時間後有多少仍被保持者，一般 而言該電壓保持率咼表不液晶顯示元件之信賴性高。 [先前技術文獻] 專利文獻 專利文獻1 :特開平7- 1 20769號公報 專利文獻2:特開平9-146100號公報 專利文獻3:特開2008-90297號公報 專利文獻4 :特開平9_2 5 8229號公報 【發明內容】 [發明所欲解決之問題] 本發明之目的在於提供摩擦時難以發生膜之剝落或傷 痕且液晶配向性良好，進而電壓保持率高之液晶配向膜， 提供可獲得該液晶配向膜之液晶配向劑，提供可獲得該液 晶配向劑之聚合物，以及提供成爲該聚合物原料之新穎二 胺化合物。再者，提供因液晶配向膜之削減或傷痕引起之 顯示缺陷少且信賴性高之液晶顯示元件。 [用以解決問題之手段] 本發明主旨如下。 [1] —種以下述式（1)表示之二胺化合物， 201202176 [化i]201202176 VI. Description of the Invention: [Technical Field] The present invention relates to a novel diamine compound which can be used as a raw material of a polymer used for a liquid crystal alignment film or the like, a polylysine obtained therefrom, and a polyimine And a liquid crystal alignment agent. Further, it relates to a liquid crystal display element having a liquid crystal alignment film obtained from the above liquid crystal alignment agent. [Prior Art] The liquid crystal alignment film which is currently used as a liquid crystal display element is mainly coated with a liquid crystal alignment agent containing a polyamidene precursor such as polyacrylamide or a soluble polyimine as a main component and fired into a coating film. Then, the liquid crystal alignment film obtained by subjecting the coating film to a rubbing treatment is performed by rubbing the surface of the coating film with the cloth. Therefore, there is a problem that the liquid crystal alignment film is provided with a scratch-reducing effect, but one of the liquid crystal display elements is used. The tendency to perform rubbing treatment under stronger conditions. The purpose is to make the liquid crystal phase state more uniform and stronger by performing a strong rubbing treatment. Therefore, the demand for the friction resistance of the liquid crystal alignment film becomes high. A method of obtaining a liquid crystal alignment film which is less likely to cause film reduction or scratching by rubbing treatment, and a method of adding various additives to a polyimide or a polyimide precursor (see, for example, Patent Document 1 and Patent Document 2) In addition to this, a polyimine structure having excellent friction resistance is also proposed (for example, refer to Patent Document 3 and Patent Document 4). Further, in order to drive the liquid crystal by voltage, the liquid crystal display element also requires electrical characteristics to the liquid crystal alignment film. Therefore, one of the representative characteristics required for the liquid crystal alignment film -5 - 201202176 is the voltage holding ratio. The voltage holding ratio indicates how much the voltage applied to the liquid cell is still held after a certain period of time. Generally, the voltage holding ratio is high in the reliability of the liquid crystal display device. [PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a liquid crystal alignment film which is less likely to cause peeling or scratching of a film during rubbing and which has good liquid crystal alignment property and high voltage holding ratio, and provides the liquid crystal. A liquid crystal alignment agent for an alignment film, a polymer which can obtain the liquid crystal alignment agent, and a novel diamine compound which is a raw material of the polymer. Further, a liquid crystal display element having less display defects due to reduction or scratches of the liquid crystal alignment film and having high reliability is provided. [Means for Solving the Problem] The gist of the present invention is as follows. [1] A diamine compound represented by the following formula (1), 201202176 [Chem. i]
r R 1 表、 双不-CH2-、-0-、-CONH-、-NHCO-、-coo-、-〇CO-或’ R2表示直鏈狀或分支狀之碳數1至碳數20之伸院 基’且該伸烷基之任意的-CH2-可經-CF2-或-CH = CH·、或 下述任~~取代基（該等基彼此不相鄰接）取代，取代基 :·〇、-NHCO- ' -CONH- ' -COO·、-OCO-、-NH-、-NHCONH-、-NHCSNH-，R3 表示-CH2-、-0-、-NH-、或伸 苯基）。 [2]如上述[1]記載之二胺化合物，其中式（1 )之R2 爲直鏈狀或分支狀之碳數2至碳數1〇之伸烷基。 其 其 [3] 如上述Π]或[2]中任一項記載之二胺化合物 中式（1)之R1爲-〇-或-C00-。 [4] 如上述[1]至[3]中任一項記載之二胺化合物 中以式（1)表示之二胺化合物爲下述任一化合物：r R 1 Table, bis-CH2-, -0-, -CONH-, -NHCO-, -coo-, -〇CO- or 'R2 represents a linear or branched carbon number of 1 to a carbon number of 20 Any of the -CH2- of the alkyl group and the alkyl group may be substituted by -CF2- or -CH=CH., or any of the following substituents (the groups are not adjacent to each other), and the substituent: ·〇, -NHCO- ' -CONH- ' -COO·, -OCO-, -NH-, -NHCONH-, -NHCSNH-, R3 for -CH2-, -0-, -NH-, or phenyl) . [2] The diamine compound according to the above [1], wherein R2 of the formula (1) is a linear or branched carbon group having 2 to a carbon number of 1 Å. [3] The diamine compound according to any one of the above [2], wherein R1 of the formula (1) is -〇- or -C00-. [4] The diamine compound represented by the formula (1) in the diamine compound according to any one of the above [1] to [3] is any one of the following compounds:
[5] —種聚合物’其係使用如上述Π]至[4]中任一項 201202176 記載之二胺化合物作爲原料之一部分合成而成。 [6] —種聚醯胺酸，其係使含有如上述[1]至[4]中任 一項記載之二胺化合物的二胺成分與四羧酸二酐成分反應 而得。 [7] 如上述[5]記載之聚醯胺酸，其中上述二胺成分 含有1 〇莫耳％以上之如上述[1 ]至[4]中任一項記載之二胺 化合物。 [8] —種聚醯亞胺，其係使如上述[6]或[7]記載之聚 醯胺酸醯亞胺化而獲得。 [9] —種液晶配向劑，其特徵爲含有如上述[6]或[7] 記載之聚醯胺酸及如上述[8]記載之聚醯亞胺中之至少一 種。 [10] —種液晶配向膜，其係使用如上述[9]記載之液 晶配向劑而得。 [1 1 ] 一種液晶顯示元件，其具備有如上述[1 0]記載 之液晶配向膜。 [發明效果] 本發明之新穎二胺化合物可使用於構成液晶配向膜之 聚合物的厚料，可獲得不損及液晶配向性、摩擦耐性及電 壓保持特性獲得提高之液晶配向膜。換言之，藉由使用利 用本發明之二胺化合物作爲原料之聚合物作爲液晶配向劑 之成分，可獲得摩擦時難以發生膜的剝落或傷痕且液晶配 向性良好，進而電壓保持率高的液晶配向膜。具備由本發 -8- 201202176 明之液晶配向劑所得之液晶配向膜之液晶顯示元件’成爲 液晶配向膜之削減或傷痕引起之顯示缺陷少且信賴性高之 液晶顯示元件。 【實施方式】 以下對本發明加以詳細說明。 <二胺化合物> 本發明之二胺化合物爲以下述通式（1)表示之化合 物’其特徵爲具有由間隔基部位與末端乙烯基所成之側鏈 [化3][5] A polymer which is synthesized by using, as a raw material, a diamine compound as described in any one of the above-mentioned items [02]. [6] A poly-proline which is obtained by reacting a diamine component containing the diamine compound according to any one of the above [1] to [4] with a tetracarboxylic dianhydride component. [7] The polyamine derivative according to the above [5], wherein the diamine component contains 1% by mole or more of the diamine compound according to any one of the above [1] to [4]. [8] A polyimine which is obtained by imidating a polyphosphonium hydrazide as described in [6] or [7] above. [9] A liquid crystal alignment agent comprising at least one of the polyamic acid described in the above [6] or [7] and the polyimine according to the above [8]. [10] A liquid crystal alignment film obtained by using the liquid crystal alignment agent according to the above [9]. [1 1 ] A liquid crystal display element comprising the liquid crystal alignment film according to the above [10]. [Effect of the Invention] The novel diamine compound of the present invention can be used for a thick material of a polymer constituting a liquid crystal alignment film, and a liquid crystal alignment film which can improve the liquid crystal alignment property, the friction resistance and the voltage holding property can be obtained. In other words, by using a polymer using the diamine compound of the present invention as a raw material component as a component of the liquid crystal alignment agent, it is possible to obtain a liquid crystal alignment film which is less likely to cause peeling or scratching of the film during rubbing and which has good liquid crystal alignment property and high voltage holding ratio. . The liquid crystal display element ’ which is a liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention is a liquid crystal display element which has a small reduction in display defects due to reduction of a liquid crystal alignment film or a scratch. [Embodiment] Hereinafter, the present invention will be described in detail. <Diamine compound> The diamine compound of the present invention is a compound represented by the following formula (1), which is characterized by having a side chain formed by a spacer moiety and a terminal vinyl group.
R1—R2—R3一C=CH2 Η (1) 式（1 )中之Rtl^-R3爲側鏈中之間隔基部位（連接 末端乙烯基與二胺基苯骨架之基），Ri表示該間隔基部位 中與二胺基苯骨架之鍵結基。R1係自_Cii2-(亞甲基）、-〇·(酸基）、-CONH-(醯胺基）、-NHC0_ (反醯胺基） 、_c〇〇-(酯基）、-OCO-(反酯基）及-NH-(胺基）中 所出者。Ri可藉—般有機合成方法形成，但就合成容易性 之觀點而言，較佳爲-CH2-、-〇-、-coo-、-NHCO-或-NH-’更好爲-0-或- COO-。 式（1 )中之R2係成爲間隔基部位之中心的部分，爲 -9- 201202176 直鏈狀或分支狀之碳數1至碳數20之伸烷基。但，伸烷基 之任意-CH2-可經-CF2-或-CH = CH-取代。且經取代之-CH2-可於一個部位亦可爲複數個部位。 再者，該伸烷基之任意-CH2-亦可經-O-'-NHCO-、-CONH-、-COO·、-OCO- ' -NH-、-NHCONH-、-NHCSNH-之取代基取代。但該等取代基互不相鄰》此意指R2亦可包 含伸烷基-取代基-伸烷基之構成。此外，R1爲-CH2 -時， 意指R2中之R1側之末端亦可爲該取代基。 同樣地，R3爲下述-CH2-或伸苯基時，意指R2中之R3 側之末端亦可爲該取代基》因此，R1爲-CH2-且R3爲-CH2-或伸苯基時，意指R2可爲取代基-伸苯基-取代基之構成或 亦可爲上述取代基之任一者。又以上述取代基取代之-CH2-可爲一個部位亦可爲複數個部位。 其中就合成容易性之觀點而言，上述R2較好爲碳數2 至碳數10，更好爲碳數2至碳數6之伸烷基。 式（1 )中之R3表示間隔基部位中與末端乙烯基之鍵 結基。R3係自-CH2-、-0-、-NH-及伸苯基中選出》其中， 就合成容易性之觀點而言，較好爲-CH2-或-0· » 式（1 )中之兩個胺基（-NH2 )之鍵結位置並無限定 。兩個胺基之具體位置，相對於苯環上之R1鍵結位置，舉 例爲2,3之位置、2,4之位置、2,5之位置、2,6之位置、3,4 之位置、3,5之位置。本發明之二胺化合物作爲聚合物之 原料使用時，由胺基反應性之觀點觀之，較好爲2,4之位 置、2,5之位置或3,5之位置。若亦考慮合成二胺化合物時 -10- 201202176 之容易性，則更好爲2,4之位置或3,5之位置。 以下雖例示本發明二胺化合物之較佳例，但並不限定 於此。 [化4]R1—R2—R3—C=CH2 Η (1) Rtl^-R3 in the formula (1) is a spacer moiety in the side chain (the base of the terminal vinyl group and the diaminobenzene skeleton), and Ri represents the interval. A bond group with a diaminobenzene skeleton in the base portion. R1 is derived from _Cii2-(methylene), -〇(acid group), -CONH-(nonylamino), -NHC0_ (reverse amide), _c〇〇-(ester group), -OCO- (reverse ester group) and -NH- (amine group). Ri can be formed by a general organic synthesis method, but from the viewpoint of ease of synthesis, it is preferably -CH2-, -〇-, -coo-, -NHCO- or -NH-' is preferably -0- or - COO-. R2 in the formula (1) is a portion which becomes a center of the spacer portion, and is a linear or branched carbon group having 1 to 20 carbon atoms in the range of -9 to 201202176. However, any -CH2- of the alkyl group may be substituted by -CF2- or -CH=CH-. And the substituted -CH2- may be a plurality of parts in one part. Furthermore, any -CH2- of the alkylene group may also be substituted by a substituent of -O-'-NHCO-, -CONH-, -COO., -OCO-'-NH-, -NHCONH-, -NHCSNH- . However, the substituents are not adjacent to each other. This means that R2 may also comprise a stretch alkyl-substituent-alkylene group. Further, when R1 is -CH2-, it means that the terminal of the R1 side in R2 may be the substituent. Similarly, when R3 is -CH2- or a phenyl group, it means that the terminal of the R3 side in R2 may also be the substituent. Therefore, when R1 is -CH2- and R3 is -CH2- or phenyl group And means that R2 may be a substituent-phenylene-substituted group or may be any of the above substituents. Further, -CH2- substituted by the above substituent may be a single site or a plurality of sites. Among them, R2 is preferably a carbon number of 2 to a carbon number of 10, more preferably a carbon number of 2 to a carbon number of 6 alkyl groups, from the viewpoint of easiness of synthesis. R3 in the formula (1) represents a bond group to the terminal vinyl group in the spacer moiety. R3 is selected from -CH2-, -0-, -NH- and phenylene. Among them, from the viewpoint of easiness of synthesis, it is preferably -CH2- or -0· » two of formula (1) The bonding position of the amine group (-NH2) is not limited. The specific positions of the two amine groups are, for example, the position of 2, 3, the position of 2, 4, the position of 2, 5, the position of 2, 6, and the position of 3, 4 with respect to the R1 bonding position on the benzene ring. , 3, 5 position. When the diamine compound of the present invention is used as a raw material of a polymer, it is preferably at a position of 2, 4, 2, 5 or 3, 5 from the viewpoint of amine reactivity. If the ease of synthesizing the diamine compound -10- 201202176 is also considered, it is more preferably the position of 2, 4 or the position of 3, 5. Although preferred examples of the diamine compound of the present invention are exemplified below, it is not limited thereto. [Chemical 4]
上述所示之式中，Χι表示-CH2-、-0-、-CONH-、-NHCO-、-COO-、-OCO-或-NH-，X2 表示-CH2-、-〇·或· NH-，X3 表示0-、-NHCO-、-CONH-、-COO-、-〇c〇_ 或_ NH-，X4 表示-CH2-、-0、-CONH-、-NHCO-、-COO-、_ OCO-或-NH-。n表示1〜20之整數，nl及n2各獨立表示卜18 之整數，但nl及n2之合計爲2〜19。n3、n4及n5各獨立表示 1〜19之整數，但n3、n4及n5之合計爲3〜21» n6表示1〜19之 整數。 <二胺化合物之合成方法> 合成以前述式（1)表示之二胺化合物之方法並無特 別限制，但可例如使以下述式（2 )表示之二硝基化合物 -11 - (2) 201202176 之硝基還原轉變成胺基而得 [化5] o2n ο2νIn the above formula, Χι denotes -CH2-, -0-, -CONH-, -NHCO-, -COO-, -OCO- or -NH-, and X2 represents -CH2-, -〇· or · NH- , X3 represents 0-, -NHCO-, -CONH-, -COO-, -〇c〇_ or _ NH-, X4 represents -CH2-, -0, -CONH-, -NHCO-, -COO-, _ OCO- or -NH-. n represents an integer of 1 to 20, and nl and n2 each independently represent an integer of 卜18, but the total of nl and n2 is 2 to 19. N3, n4 and n5 each independently represent an integer of 1 to 19, but the total of n3, n4 and n5 is 3 to 21»n6 represents an integer of 1 to 19. <Synthesis Method of Diamine Compound> The method of synthesizing the diamine compound represented by the above formula (1) is not particularly limited, but for example, the dinitro compound 11 - (2) represented by the following formula (2) can be used. ) 201202176 nitro reduction is converted to an amine group to obtain [chemical 5] o2n ο2ν
R1—R2—R3—C—CH7 Η (式（2 )中之R1、R2及R3與式（1 )之定義相同）。 使上述二硝基化合物還原之方法，爲了不使末端之雙 鍵反應，舉例有使用鈀-碳、氧化鉑、阮尼鎳、鉑黑、铑_ 氧化鋁、硫化鉑碳、錫、鐵等作爲觸媒，於以酸乙酯、甲 苯、四氫呋喃、二噁烷、醇系等溶劑中，利用氫氣、聯胺 、氯化氫等進行之還原方法。 以上述式（2)表示之二硝基化合物可藉由對於二硝 基苯透過R1使-R2-R3鍵結之方法而獲得。例如R1爲醯胺鍵 (-CONH-)時，可舉例爲使二硝基苯之醯氯與具有R2及 R3之胺基化合物在鹼存在下反應之方法。且，R1爲反醯胺 鍵（-NHCO-)時，舉例爲使含有胺基之二硝基苯與具有 R2及R3之醯氯在鹼存在下反應之方法。 R1爲酯鍵（-COO-)時，舉例有使二硝基苯之醯氯與 具有R2及R3之醇化合物在鹼存在下反應之方法。且R1爲反 酯鍵（-OCO-)時，舉例有使含有羥基之二硝基苯與具有 R2及R3之醯氯在鹼存在下反應之方法。 R1爲醚鍵（-0-)時，舉例有使含有鹵基之二硝基苯 與具有R2及R3之醇化合物在鹼存在下反應之方法。 R1爲胺基（-NH-)時，舉例有使含有鹵基之二硝基苯 -12- 201202176 與具有R2及R3之胺基化合物在鹼存在下反應之方法。 R1爲碳-碳鍵（-CH2-)時，舉例有使含有鹵基之二硝 基苯與具有R2及R3之具有不飽和鍵之化合物利用Heck反應 或Sonogashira交聯反應而反應之方法。 作爲上述二硝基苯之醯氯舉例有3,5-二硝基苯甲醯氯 、2,4-二硝基苯甲醯氯、3,5-二硝基苄基氯、2,4-二硝基 苄基氯等。且，作爲含有胺基之二硝基苯舉例有2,4-二硝 基苯胺、3,5-二硝基苯胺、2,6-二硝基苯胺等。 作爲含有羥基之二硝基苯舉例有2,4-二硝基苯酚、 3.5- 二硝基苯酚、2,6-二硝基苯酚等》 作爲含有鹵基之二硝基苯舉例有2,4-二硝基氟苯、 3.5- 二硝基氟苯、2,6-二硝基氟苯、2,4-二硝基碘苯、3,5-二硝基碘苯、2，6-二硝基碘苯等。 至於上述反應所用之鹼，舉例有三乙胺、吡啶、碳酸 鈉、碳酸鉀、碳酸氫鈉等。 <聚合物> 本發明之聚合物爲以前述式（1)表示之二胺化合物 (以下亦稱爲特定二胺化合物）作爲原料之—部分所合成 者。例如，使包含特定二胺化合物之二胺成分與四羧酸二 酐成分或其二酯體成分進行聚合反應而得之聚醯胺酸及聚 醯胺酸酯，使該等聚醯胺酸脫水閉環所得之聚醯亞胺，使 二胺成分與二羧酸氯成分或四羧酸氯成分進行聚合反應所 得之聚醯胺或聚醯胺酸等。 -13- 201202176 <聚醯胺酸> 本發明之聚醯胺酸中，特定二胺化合物可爲上述聚合 反應中使用之二胺成分之全部，亦可與其他二胺化合物倂 用。且所使用之特定二胺化合物可爲一種，亦可爲兩種以 上。 特定二胺化合物與其他二胺化合物併用時，特定二胺 化合物之使用比例並無特別限制，但特定二胺化合物之比 例越多，更顯著地發揮使用特定二胺之效果。特定二胺化 合物之較佳比例若一定要顯示，則較好爲聚合反應中使用 之二胺成分之10莫耳％以上爲特定二胺化合物。再者，較 好二胺成分之30莫耳％以上爲特定二胺化合物，更好爲50 莫耳％以上。 與特定二胺化合物倂用之其他二胺化合物並未特別限 制’但可舉例爲例如下述式（3)中之B爲下述表丨〜表4所 示之二價有機基之化合物。 [化6] H2N— B — NH2 ⑶ -14- 201202176 [表1] B*1 B-2 众 Β·3 xm B-4 HX〇X3 B-5 Η;σχς Β*6 B-7 普 B-8 众 Β·9 XT B-10 o-ch3 B-ll Β-12 h3c _Vch3 善 B-13 众C〇〇H B-14 j^COOH XX Β-15 ^ COOH B.16 ch3 B-17 众Cl Β-18 Cl Cl· B-19 、ch3 B-20 Β*21 fi-m B*22 B-23 xr Β*24 B-25 xr^ B-26 Β·27 a B-28 -ΟΌ- B-29 h3c ch3 Β·30 CHj h3c 201202176 [表2]R1 - R2 - R3 - C - CH7 Η (R1, R2 and R3 in the formula (2) are the same as defined in the formula (1)). The method for reducing the above dinitro compound is, for example, using palladium-carbon, platinum oxide, nickel iridium nickel, platinum black, rhodium ruthenium oxide, platinum sulfide carbon, tin, iron, or the like in order not to react the double bond at the terminal. The catalyst is a reduction method using hydrogen, a hydrazine, hydrogen chloride or the like in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol. The dinitro compound represented by the above formula (2) can be obtained by a method in which -R2-R3 is bonded to dinitrobenzene through R1. For example, when R1 is a guanamine bond (-CONH-), a method of reacting ruthenium chloride of dinitrobenzene with an amine compound having R2 and R3 in the presence of a base can be exemplified. Further, when R1 is a ruthenium amine bond (-NHCO-), a method of reacting an amine group-containing dinitrobenzene with a ruthenium chloride having R2 and R3 in the presence of a base is exemplified. When R1 is an ester bond (-COO-), a method of reacting ruthenium chloride of dinitrobenzene with an alcohol compound having R2 and R3 in the presence of a base is exemplified. Further, when R1 is a transester bond (-OCO-), a method of reacting a dinitrobenzene having a hydroxyl group with a phosphonium chloride having R2 and R3 in the presence of a base is exemplified. When R1 is an ether bond (-0-), a method of reacting a dinitrobenzene containing a halogen group with an alcohol compound having R2 and R3 in the presence of a base is exemplified. When R1 is an amine group (-NH-), a method of reacting a dinitrobenzene-12-201202176 containing a halogen group with an amine compound having R2 and R3 in the presence of a base is exemplified. When R1 is a carbon-carbon bond (-CH2-), a method of reacting a dinitrobenzene having a halogen group with a compound having an unsaturated bond having R2 and R3 by a Heck reaction or a Sonogashira crosslinking reaction is exemplified. Examples of the above-mentioned dinitrobenzene ruthenium chloride include 3,5-dinitrobenzimid chloride, 2,4-dinitrobenzhydryl chloride, 3,5-dinitrobenzyl chloride, and 2,4-. Dinitrobenzyl chloride and the like. Further, examples of the dinitrobenzene containing an amine group include 2,4-dinitroaniline, 3,5-dinitroaniline, and 2,6-dinitroaniline. Examples of the dinitrobenzene having a hydroxyl group include 2,4-dinitrophenol, 3.5-dinitrophenol, 2,6-dinitrophenol, etc. As the dinitrobenzene having a halogen group, 2, 4 are exemplified. -dinitrofluorobenzene, 3.5-dinitrofluorobenzene, 2,6-dinitrofluorobenzene, 2,4-dinitroiodobenzene, 3,5-dinitroiodobenzene, 2,6-di Nitroiodobenzene and the like. As the base to be used in the above reaction, there may be mentioned, for example, triethylamine, pyridine, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or the like. <Polymer> The polymer of the present invention is a mixture of a diamine compound represented by the above formula (1) (hereinafter also referred to as a specific diamine compound) as a raw material. For example, polylysine and polylysine obtained by polymerizing a diamine component containing a specific diamine compound and a tetracarboxylic dianhydride component or a diester component thereof, and dehydrating the polyglycine The polyimine obtained by ring closure, a polyamine or a polyamine obtained by polymerizing a diamine component with a dicarboxylic acid chloride component or a tetracarboxylic acid chloride component. -13-201202176 <Polyuric acid> In the polyglycine of the present invention, the specific diamine compound may be all of the diamine components used in the above polymerization reaction, and may be used together with other diamine compounds. Further, the specific diamine compound to be used may be one type or two or more types. When the specific diamine compound is used in combination with other diamine compounds, the ratio of use of the specific diamine compound is not particularly limited, but the more the ratio of the specific diamine compound, the more remarkable the effect of using a specific diamine. When a preferred ratio of the specific diamine compound is necessarily exhibited, it is preferred that 10 mol% or more of the diamine component used in the polymerization reaction is a specific diamine compound. Further, more than 30 mol% of the diamine component is preferably a specific diamine compound, more preferably 50 mol% or more. The other diamine compound to be used in combination with the specific diamine compound is not particularly limited, but for example, a compound of the following formula (3) wherein B is a divalent organic group shown in the following Tables to Table 4 can be exemplified. H2N— B — NH2 (3) -14- 201202176 [Table 1] B*1 B-2 Public Β·3 xm B-4 HX〇X3 B-5 Η; σχς Β*6 B-7 General B- 8 众Β·9 XT B-10 o-ch3 B-ll Β-12 h3c _Vch3 善B-13 众 C〇〇H B-14 j^COOH XX Β-15 ^ COOH B.16 ch3 B-17 Β-18 Cl Cl· B-19 , ch3 B-20 Β*21 fi-m B*22 B-23 xr Β*24 B-25 xr^ B-26 Β·27 a B-28 -ΟΌ- B- 29 h3c ch3 Β·30 CHj h3c 201202176 [Table 2]
B-31 f3c’ Β·32 jCOX Β·33 iTXX Β·34 χτα Β·35 χΛα Β*36 j/a Β*37 Β·38 Β.39 Β-40 hjcchj Β·41 F3Q.CF=3 ιΛχ Β·42 Β-43 Η 人 Β*44 -φ〇Γ Β-45 Β·46 Β*47 -〇ζ°~ Β*48 Β-49 Β*50 Β-51 -Qr^Qr Β-52 V Β·53 Β-54 iX -16- 201202176 [表3]B-31 f3c' Β·32 jCOX Β·33 iTXX Β·34 χτα Β·35 χΛα Β*36 j/a Β*37 Β·38 Β.39 Β-40 hjcchj Β·41 F3Q.CF=3 ιΛχ Β ·42 Β-43 Η人Β*44 -φ〇Γ Β-45 Β·46 Β*47 -〇ζ°~ Β*48 Β-49 Β*50 Β-51 -Qr^Qr Β-52 V Β· 53 Β-54 iX -16- 201202176 [Table 3]
Β·55 B*56 -QrOrO~ Β-57 Φο B-58 Β-59 B-60 ;〇rW Β-6Ι OTW B-62 Β-63 公％σ F B-64 H3c ch3 IT 人。XX Β·65 Η^νεΗ3 B-66 Β-67 xxjykxxr B-68 Β-69 ——(CH2)n—— n = 2 〜12 B-70 ch3 —(CH2)+(CH2)2 - ch3 Β-71 ch3 一(CH2)4-C—(CH2)3— ch3 B-72 ch3 ch3 -CH2-C-(CH2)2-C-(CH2)2-H H Β*73 ch3 ch3 _ ch2_c—(cny 2-c _ (ch 2)3— Η H B.74 CH3 一(CH^2"C—(CH2)5— H -17- 201202176 [表4] B-75 CH3 —(CH2)4-C-(CH2)5-H Β-76 —(C Η2)3-〇 -(CH2)2-〇 -(CHj) J- B-77 CH, CHj 一 (CHJj—Si—0—Si—(CHJj— CHj CH3 Β·78 —(CH2)n-^^— ^ n = 3~12 Β·79 Β-80 n = 2〜12 n = 2~12 Β_81 Β·82 η = 2〜12 n = 2~12 上述聚醯胺酸之合成中，與如上述之二胺成分聚合反 應之四羧酸二酐成分並無特別限制。且四羧酸二酐成分中 所含之四羧酸二酐可爲一種，亦可爲兩種以上。若欲舉例 可使用於上述聚合反應之四羧酸二酐具體例，則可舉例有 下述式（4)中之A爲下述表5及表6所示之四價有機基之 化合物。 [化7]Β·55 B*56 -QrOrO~ Β-57 Φο B-58 Β-59 B-60 ;〇rW Β-6Ι OTW B-62 Β-63 %%σ F B-64 H3c ch3 IT person. XX Β·65 Η^νεΗ3 B-66 Β-67 xxjykxxr B-68 Β-69 ——(CH2)n——n = 2 ～12 B-70 ch3 —(CH2)+(CH2)2 - ch3 Β- 71 ch3 I(CH2)4-C-(CH2)3—ch3 B-72 ch3 ch3 -CH2-C-(CH2)2-C-(CH2)2-HH Β*73 ch3 ch3 _ ch2_c—(cny 2 -c _ (ch 2)3— Η H B.74 CH3 I (CH^2"C—(CH2)5—H -17- 201202176 [Table 4] B-75 CH3 —(CH2)4-C-( CH2)5-H Β-76 —(C Η2)3-〇-(CH2)2-〇-(CHj) J- B-77 CH, CHj I (CHJj—Si—0—Si—(CHJj—CHj CH3 Β·78 —(CH2)n-^^— ^ n = 3~12 Β·79 Β-80 n = 2~12 n = 2~12 Β_81 Β·82 η = 2~12 n = 2~12 In the synthesis of the proline, the tetracarboxylic dianhydride component which is polymerized with the diamine component as described above is not particularly limited, and the tetracarboxylic dianhydride contained in the tetracarboxylic dianhydride component may be one type. In order to exemplify a specific example of the tetracarboxylic dianhydride used in the above polymerization reaction, A in the following formula (4) is a tetravalent organic substance shown in Tables 5 and 6 below. a compound of the base. [Chem. 7]
-18- 201202176 [表5] A.l A，2 H3C ch3 A-3 h3c ch3 A_4 h3c ch3 、一， ---、 h3c ch3 Α·5 ΤΓ A*6 rc A_7 女 Α·8 rc A-9 XC A-10 All A-12 me A-13 A-14 ^φχ ΑΊ5 A-16 ΑΊ7 ΑΊ8 ch3 A-19 A*20 D-PV A-21 V ch5 A-22 A-23 A.-24 >oc A_25 71： Α·26 )DC A.27 XXX A-28 A-29 A-30 -19- 201202176-18- 201202176 [Table 5] Al A,2 H3C ch3 A-3 h3c ch3 A_4 h3c ch3 , one, ---, h3c ch3 Α·5 ΤΓ A*6 rc A_7 Nuwa 8 rc A-9 XC A -10 All A-12 me A-13 A-14 ^φχ ΑΊ5 A-16 ΑΊ7 ΑΊ8 ch3 A-19 A*20 D-PV A-21 V ch5 A-22 A-23 A.-24 >oc A_25 71: Α·26)DC A.27 XXX A-28 A-29 A-30 -19- 201202176
[表6] A-31 Α.32 Α.33 xrtc Α·34 Α·35 χΛχ Α·36 Α-37 Xikx Α·38 Α·39 Α-40 OX Α·41 οχ Α·42 Α-43 Α*44 CHj ybjc h3c’ Α·45 ch3 H,C 利用二胺成分與四羧酸二酐成分反應獲得聚醯胺酸可 使用公知之合成方法。至於代表性者，有於有機溶劑中混 合二胺成分及四羧酸二酐成分之方法。依據該方法，二胺 化合物與四羧酸二酐之反應在有機溶劑中較容易進行，且 不發生副產物方面亦較有利。 上述反應中使用之有機溶劑若爲可熔解所生成之聚醯 胺酸者則無特別限定。再者，即使爲不溶解聚醯胺酸之有 機溶劑，在不使所生成聚醯胺酸析出之範圍內，亦可於上 述溶劑中混合使用。且有機溶劑中之水分會阻礙聚合反應 ，進而成爲使生成之聚醯胺酸水解之原因，故較好使用有 機溶劑經脫水乾燥者。 以下舉例有機溶劑之具體例。 N，N-二甲基甲醯胺、N，N-二甲基乙醯胺、N，N-二乙基 -20- 201202176 甲醯胺、N-甲基甲醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、2 -吡咯烷酮、l，3 -二甲基-2·咪唑啉嗣、3 -甲氧 基-N，N-二甲基丙基醯胺、N_甲基己內醯胺、二甲基亞颯 、四甲基脲、吡啶、二甲基楓、六甲基亞颯、丁內酯 、異丙醇、甲氧基甲基戊醇、二戊烯、乙基戊基酮、甲基 壬基酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、甲 基溶纖素、乙基溶纖素、甲基溶纖素乙酸酯、丁基溶纖素 乙酸酯、乙基溶纖素乙酸酯、丁基卡必醇、乙基卡必醇、 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、丙二醇單 丁醚、丙二醇第三丁醚、二丙二醇單甲醚、丙二醇單甲醚 乙酸酯、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲醚 、二乙二醇二***、二丙二醇單乙酸酯單甲醚、二丙二醇 單甲醚、二丙二醇單***、二丙二醇單乙酸酯單***、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、乙基異丙醚、二異丁烯、乙酸戊酯、丁酸丁 酯、丁醚、二異丁酮、甲基環己烯、丙醚、二己醚、二噁 烷、正己烷、正庚烷、正辛烷、二***、環己酮、碳酸乙 烯酯、碳酸丙烯酯、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙 酸乙酯、乙酸正丁酯、乙酸丙二醇單***、丙酮酸甲酯、 丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯 、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3·甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、二甘醇二甲醚、4- -21 - 201202176 羥基-4-甲基-2_戊酮、2_乙基-1-己酮。該等有機溶劑可單 獨使用亦可混合使用。 二胺成分與四羧酸二酐成分在有機溶劑中反應時，舉 例有將二胺成分分散或溶解於有機溶劑中之溶液予以攪拌 ，直接添加四羧酸二酐或分散或溶解於有機溶劑中再添加 之方法，相反地於使四羧酸二酐溶解或分散於有機溶劑中 之溶液中添加二胺成分之方法，進而使四羧酸二酐成分與 二胺成分交替添加之方法等。可使用該等之任一方法。且 二胺成分或四羧酸二酐成分係由複數種化合物構成時，亦 可預先以混合狀態反應，亦可個別依次反應，進而亦可使 個別反應之低分子量物混合並反應爲高分子量物。 二胺成分與四羧酸二酐成分反應時之溫度可選擇任意 溫度，例如在- 20°C〜150°C，較好爲- 5°C〜l〇〇°C之範圍。 且反應可以任意濃度進行，例如卜50質量％，較好爲5〜30 質量°/〇。 上述聚合反應中，以（四羧酸二酐成分之合計莫耳數 /二胺成分合計莫耳數）表示之莫耳比例可依據欲獲得之 聚醯胺酸分子量選擇爲任意値。與一般聚縮合反應同樣， 該莫耳比例越接近1.0則生成之聚醯胺酸分子量越大。若 欲顯示莫耳比例之較佳範圍，則爲0.8〜1.2。 <聚醯亞胺> 聚醯亞胺可使上述聚醯胺酸進行脫水閉環（醯亞胺化 )而獲得。使聚醯胺酸醯亞胺化之方法，舉例有使聚醯胺 -22- 201202176 酸溶液直接加熱之熱醯亞胺化、於聚醯胺酸溶液中添加觸 媒之觸媒醯亞胺化。 聚醯胺酸於溶液中進行熱醯亞胺化時之溫度爲loot 〜400 °c ’較好爲120°C〜25 0 °c，較好爲邊進行將由醯亞胺 化反應生成之水排出至系統外之方法。 聚醯胺酸之觸媒醯亞胺化，可藉由在聚醯胺酸溶液中 添加鹼性觸媒及酸酐，在-2 0°C〜2 5 0°C，較好在0°C〜180°C 攪拌而進行。鹼性觸媒之量爲醯胺酸基之0.5〜3 0莫耳倍， 較好爲2〜20莫耳倍，酸酐量爲醯胺酸基之丨〜“莫耳倍，較 好爲3〜30莫耳倍。作爲鹼性觸媒可舉例有吡啶、三乙胺、 三甲胺、三丁胺、三辛胺等，其中吡啶具有使反應進行之 適度鹼性故而較佳。至於酸酐可舉例有乙酸酐、偏苯三甲 酸酐、均苯四甲酸酐等，其中若使用乙酸酐則反應結束後 之純化變容易故較佳。由觸媒醯亞胺化之醯亞胺化率可藉 由調整觸媒量、反應溫度、反應時間等而控制。 本發明之聚醯亞胺中，由聚醯胺酸之脫水閉環率（醯 亞胺化率）並無必要必須爲1 00%。 自聚醯胺酸或聚醯亞胺反應溶液回收所生成之聚胺酸 或聚醯亞胺時’只要於反應溶液中投入弱溶劑並沉澱即可 。沉澱中所用之弱溶劑可舉例爲甲醇、丙酮、己烷、丁基 溶纖素、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯 、苯、水等。投入至弱溶劑中並沉澱之聚合物可經過濾回 收後，於常壓或減壓下，於常溫或經加熱而乾燥。且，沉 澱回收之聚合物若再溶解於有機溶劑中，重複進行2〜10次 -23- 201202176 之再沉澱回收操作，則可減少聚合物中之不純物。此時之 弱溶劑，舉例有例如醇類、酮類、烴類等，若從該等內選 擇3種類以上之弱溶劑使用，則可更提高純化效率。 <液晶配向劑> 本發明之液晶配向劑爲用以形成液晶配向膜之塗佈液 ，爲將用以形成液晶配向膜之樹脂成分溶解於有機溶劑中 之溶液。此處之樹脂成分包含由前述本發明之聚合物選出 之至少一種類之聚合物。液晶配向劑中之樹脂成分含量較 好爲1質a %〜20質量％，更好爲3質量％〜15質量％，最好爲 3~10質量％。 本發明之液晶配向劑中，前述樹脂成分可全部爲本發 明之聚合物，亦可於本發明聚合物中混合其他聚合物。混 合其他聚合物時，該其他聚合物之含量較好爲樹脂成分全 體之〇 . 5質量％〜1 5質量％，更好爲1質量1 0質量。/〇。該其 他聚合物舉例爲例如不含特定二胺之二胺成分與四羧酸二 酐成分所得之聚醯胺酸或聚醯亞胺等。 本發明之液晶配向劑中所含之聚合物分子量，若考慮 由其所得之塗膜強度以及塗膜形成時之作業性、塗膜均一 性等時，藉GPC (凝膠滲透層析）法所測定重量平均分子 量較好爲5,000〜1,000,000，更好爲 10,000~150,000。 本發明之液晶配向劑中所用之有機溶劑，若爲可溶解 上述樹脂成分之有機溶劑，則無特別限制。該有機溶劑可 爲一種有機溶劑亦可爲兩種以上之混合溶劑。若要舉例有 -24- 201202176 機溶劑之具體例，可舉例爲於前述聚醯胺酸合成中所例示 之有機溶劑。其中由樹脂溶解性之觀點而言，較好爲N·甲 基-2-吡咯烷酮、τ-丁內酯、N -乙基-2-吡咯烷酮、1，3 -二 甲基-2-咪唑啉酮及3-甲氧基-N，N-二甲基丙醯胺。 又’以下所示之溶劑，由於可提高塗膜之均一性獲平 滑性，故較好混合於樹脂成分熔解性高之溶劑中而使用。 例如異丙醇、甲氧基甲基戊醇、甲基溶纖素、乙基溶纖素 、丁基溶纖素、甲基溶纖素乙酸酯、丁基溶纖素乙酸酯、 乙基溶纖素乙酸酯、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 、丙二醇單丁醚、丙二醇第三丁醚、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、二乙二醇 二***、二丙二醇單乙酸酯單甲醚、二丙二醇單甲醚、丙 二醇單甲醚乙酸酯、二丙二醇單***、二丙二醇單乙酸酯 單***、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、乙基異丙醚、二異丁烯、乙酸戊酯 、丁酸丁酯、丁醚、二異丁酮、甲基環己烯、丙醚、二己 醚、正己烷、正庚烷、正辛烷、二***、乳酸甲酯、乳酸 乙酯、乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸丙二醇單 ***、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯' 3-乙氧基丙酸甲基乙酯、3·甲氧基丙酸乙酯、3-乙氧基丙酸 、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3·甲氧基丙酸丁酯 -25- 201202176 、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧: 、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇 、丙二醇-1-單甲醚-2-乙酸酯、丁二醇-1-單*** 、二丙二醇、2-(2-乙氧基丙氧基）丙醇、乳酸 酸乙酯、乳酸正丙酯、乳酸正丁酯、乳酸異戊 基-1-己醇等。該等有機溶劑可混合複數種使用 等溶劑時，較好爲液晶配向劑中所含溶劑全體之 %，更好爲20〜60質量％。 本發明之液晶配向劑亦可含有上述以外之成 其例，舉例有提高塗佈液晶配向劑時之膜厚均一 平滑性之化合物、提高液晶配向膜與基板之密著 物等。 至於提高液晶配向膜之膜厚均一性或表面平 合物舉例有氟系界面活性劑、矽氧系界面活性劑 系界面活性劑等。更具體而言，舉例有例 EF301、EF3 03、EF3 52 ( TOKEMU PRODUCTS公 MEGAFAC F171、F173、R-30 (大日本油墨公 FLUORAD FC430、FC43 1 (住友 3M公司製）、 GUARD AG710、SUNFLON S-3 82、SC 101、 SC103、 SC104、 SC105、 SC106(旭硝子公司製 用該等界面活性劑時，其使用比例相對於液晶配 含之樹脂成分100質量份較好爲0.01〜2質量份 0.0 1 ~ 1質量份》 至於提高液晶配向膜與基板之密著性之化合 基-2-丙醇 二乙酸酯 -2-乙酸酯 甲酯、乳 酯、2-乙 。使用該 5〜80質量 分。作爲 性或表面 性之化合 滑性之化 、非離子 ]EF TOP 司製）、 司製）、 ASHAHI SC102 、 )等。使 向劑中所 ，更好爲 物之具體 -26- 201202176 例，舉例有含官能性矽烷化合物、含環氧基之化 舉例有例如3-胺基丙基三甲氧基矽烷、3-胺基丙 基砂院、2-胺基丙基三甲氧基砂院、2-胺基丙基 矽烷、N- ( 2-胺基乙基）-3-胺基丙基三甲氧基 (2-胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、 基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、 基-3-胺基丙基三甲氧基矽烷、N-乙氧羰基-3-胺 乙氧基矽烷、N -三乙氧基矽烷基丙基三伸乙三胺 氧基矽烷基丙基三伸乙三胺、10-三甲氧基矽院 三氮雜癸烷、10-三乙氧基-1，4,7-三氮雜癸烷、 基矽烷基-3，6-二氮雜壬基乙酸酯、9-三乙氧基矽 二氮雜壬基乙酸酯、N-苄基-3-胺基丙基三甲氧 N-苄基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺 甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷 氧伸乙基）-3-胺基丙基三甲氧基矽烷、N-雙（ )-3-胺基丙基三乙氧基矽烷、乙二醇二縮水甘 乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三 縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇 油醚、1，6-己二醇二縮水甘油醚、丙三醇二縮水 2.2- 二溴新戊基二醇二縮水甘油醚、1，3,5,6-四 基·2,4-己二醇、N,N，N’，N’-四縮水甘油基-間·甲 1.3- 雙（Ν，Ν·二縮水甘油基胺基甲基）環 1^小，：^’，：^’-四縮水甘油基-4,4’-二胺基二苯基甲 Ν-烯丙基-Ν-縮水甘油基）胺基丙基三甲氧基矽 合物等。 基三乙氧 三乙氧基 矽烷、Ν-3 脲基丙 Ν-乙氧羰 基丙基三 、：ΝΝ三甲 基-1，4,7-9-三甲氧 烷基-3,6-基矽烷、 基丙基三 、Ν-雙（ 氧伸乙基 油醚、聚 丙二醇二 二縮水甘 甘油醚、 縮水甘油 苯二胺、 I己烷、 烷、3-( 烷、3-( -27- 201202176 N，N-二縮水甘油基）胺基丙基三甲氧基矽烷等。 又，爲了進一步提高使用本發明之液晶配向劑所得之 液晶配向膜之摩擦耐性，亦可添加2,2’-雙（4-羥基-3,5·二 羥基甲基苯基）丙烷、四（甲氧基乙基）雙苯酚等之酚化 合物。使用該等化合物時，相對於液晶配向劑中所含樹脂 成分1〇〇質量份，較好爲0.1〜30質量份，更好爲1〜20質量 份。 本發明之液晶配向劑中，除上述以外，在不損及本發 明效果之範圍內，亦可添加用以改變液晶配向膜之介電率 或導電性等電特性之介電體或導電物質。 <液晶配向膜·液晶顯示元件> 如上述所得之本發明之液晶配向劑可塗佈於基板上、 乾燥並燒成而成爲被膜。該被膜面藉由摩擦等之配向處理 而可作爲液晶配向膜使用。 塗佈液晶配向劑之基板若爲透明性高者則無特別限制 ，例如可使用玻璃基板等。且，於反射型液晶顯示元件中 ，亦可使用僅於單側基板爲矽晶圓等之不透明者，該情形 時，電極係使用鋁等之反射光的材料。 至於液晶配向劑之塗佈方法，舉例有例如旋轉塗佈法 、印刷法、噴墨法等。且，液晶配向劑較好以細孔徑 0.1μιη~1μιη之薄膜過濾器過濾後再塗佈。 塗佈液晶配向劑後之乾燥步驟，可爲必要亦可爲不必 要，但於自塗佈後至燒成爲止之時間對每一基板爲不一定 時，或塗佈後未立即燒成之情況，較好包含乾燥步驟。該 -28- 201202176 乾燥只要是以藉由基板等之搬送等不使塗膜形狀變化之程 度蒸發溶劑即可，關於其乾燥手段並未特別限定。若舉具 體例，則舉例有在5 0〜1 5 0 °C，較好8 0〜1 2 0 °C之加熱板上， 乾燥0.5〜30分鐘，較好1〜5分鐘之方法。 塗佈液晶配向劑後之燒成，雖可在100〜3 5 0 °C之任意 溫度進行，但較好爲120°C〜300°C，更好爲150°C〜250°C。 該燒成可藉加熱板、熱風循環爐、紅外線爐等進行。 燒成後之被膜厚度並未特別限制，但較好爲5〜3 OOnm ，更好爲10〜l〇〇nm。 摩擦處理所使用之摩擦布之材質，可舉例有棉、耐綸 、縲縈等。 本發明之液晶顯示元件係利用上述方法自本發明之液 晶配向劑獲得貼附液晶配向膜之基板後，以公知方法製作 液晶胞，作爲液晶顯示元件者。 液晶胞製作之一例若舉例，則可例示有：準備形成液 晶配向膜之一對基板，於單片基板之液晶配向膜上散布間 隔物，以使液晶配向膜面成爲內側之方式貼合另一片基板 ，減壓注入液晶並封裝之方法，或於散布有間隔物之液晶 配向膜面上滴加液晶後，貼合基板並進行封裝之方法。此 時之間隔物厚度較好爲1〜30μιη，更好爲2〜ΙΟμηι。 茲舉以下實施例更詳細說明本發明，但本發明並不限 定於此。 實施例 -29- 201202176 (實施例1 ) 2,4-二硝基-1-(4-乙烯氧基）丁氧基苯之合成 [化8][Table 6] A-31 Α.32 Α.33 xrtc Α·34 Α·35 χΛχ Α·36 Α-37 Xikx Α·38 Α·39 Α-40 OX Α·41 οχ Α·42 Α-43 Α* 44 CHj ybjc h3c' Α·45 ch3 H, C A known synthesis method can be used to obtain a polyamic acid by reacting a diamine component with a tetracarboxylic dianhydride component. As for the representative, there is a method of mixing a diamine component and a tetracarboxylic dianhydride component in an organic solvent. According to this method, the reaction of the diamine compound with the tetracarboxylic dianhydride is relatively easy to carry out in an organic solvent, and it is also advantageous in terms of no by-products. The organic solvent used in the above reaction is not particularly limited as long as it is a polymerizable hyaluronic acid. Further, even if it is an organic solvent which does not dissolve polyamic acid, it can be used in combination with the above solvent in a range in which the produced polyamic acid is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polylysine, it is preferred to use an organic solvent to be dehydrated and dried. Specific examples of the organic solvent are exemplified below. N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethyl-20- 201202176 formamide, N-methylformamide, N-methyl- 2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3,3-dimethyl-2-imidazolinium, 3-methoxy-N,N-dimethylpropylguanamine, N _Methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl maple, hexamethylarylene, butyrolactone, isopropanol, methoxymethylpentanol, dipentane Alkene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve Acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoiso Propyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethyl Glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol Ethyl ether, dipropylene glycol monoacetate 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-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isopropyl ether, diisobutylene, amyl acetate, Butyl butyrate, dibutyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-heptane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate Ester, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxypropionic acid Ester, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3·methoxypropionic acid, propyl 3-methoxypropionate, Butyl 3-methoxypropionate, diglyme, 4--21-201202176 hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanone. These organic solvents may be used singly or in combination. When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred, and tetracarboxylic dianhydride is directly added or dispersed or dissolved in an organic solvent. In addition, a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dissolved or dispersed in an organic solvent, and a method of alternately adding a tetracarboxylic dianhydride component and a diamine component, etc., are used. Any of these methods can be used. When the diamine component or the tetracarboxylic dianhydride component is composed of a plurality of compounds, it may be reacted in advance in a mixed state, or may be sequentially reacted individually, or a low molecular weight substance of an individual reaction may be mixed and reacted into a high molecular weight substance. . The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted may be any temperature, for example, in the range of - 20 ° C to 150 ° C, preferably - 5 ° C to 10 ° C. Further, the reaction can be carried out at any concentration, for example, 50% by mass, preferably 5 to 30% by mass. In the above polymerization reaction, the molar ratio expressed by (the total number of moles of the tetracarboxylic dianhydride component/the total number of moles of the diamine component) can be selected to be any enthalpy depending on the molecular weight of the polyamic acid to be obtained. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the greater the molecular weight of the produced polyamine. If the preferred range of the molar ratio is to be displayed, it is 0.8 to 1.2. <Polyimine> Polyimine is obtained by subjecting the above polyamic acid to dehydration ring closure (oxime imidization). The method for imidizing polyphosphonium amide is exemplified by thermal imidization of a polyamido-22-201202176 acid solution, and catalyzation of a catalyst by adding a catalyst to a polyaminic acid solution. . The temperature at which the polyaminic acid is subjected to thermal imidization in a solution is loot to 400 ° C. Preferably, the temperature is from 120 ° C to 25 ° C. Preferably, the water formed by the hydrazine imidization reaction is discharged. The method to the outside of the system. The phthalocyanine of the polyaminic acid can be imidized by adding a basic catalyst and an acid anhydride to the polyamidic acid solution at -2 0 ° C to 250 ° C, preferably at 0 ° C. This was carried out by stirring at 180 °C. 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 anhydride is 醯 “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ 30 moles. As the basic catalyst, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like can be exemplified, and pyridine has a moderate alkalinity for the reaction, and an acid anhydride can be exemplified. Acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc., wherein if acetic anhydride is used, the purification after the end of the reaction becomes easier, and the imidization ratio of the imidization of the oxime by the catalyst can be adjusted by touch Controlled by the amount of the medium, the reaction temperature, the reaction time, etc. In the polyimine of the present invention, the dehydration ring closure ratio (the imidization ratio) of the polyglycine is not necessarily required to be 100%. When the acid or polyimine reaction solution recovers the produced polyamine or polyimine, 'as long as a weak solvent is added to the reaction solution and precipitated. The weak solvent used in the precipitation can be exemplified by methanol, acetone, hexane. , butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene , water, etc. The polymer which is added to the weak solvent and precipitated can be recovered by filtration, dried under normal pressure or reduced pressure at normal temperature or by heating, and the polymer recovered by precipitation is redissolved in an organic solvent. By repeating the reprecipitation recovery operation of 2 to 10 times -23-201202176, the impurities in the polymer can be reduced. In this case, examples of the weak solvent include alcohols, ketones, hydrocarbons, etc., from such When three or more types of weak solvents are used, the purification efficiency can be further improved. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is a coating liquid for forming a liquid crystal alignment film, which is used to form a liquid crystal alignment film. a resin component dissolved in an organic solvent. The resin component herein comprises at least one polymer selected from the foregoing polymers of the present invention. The resin component content in the liquid crystal alignment agent is preferably 1 mass% to 20 mass%. %, more preferably from 3% by mass to 15% by mass, most preferably from 3 to 10% by mass. In the liquid crystal alignment agent of the present invention, the resin component may be all of the polymer of the present invention, and may also be used in the polymer of the present invention. Mix it When the other polymer is mixed, the content of the other polymer is preferably 5% by mass of the total of the resin component. 5 mass% to 15 mass%, more preferably 1 mass 10 mass. / 〇. Examples of the other polymer For example, the polyamine or polyimine obtained from the diamine component and the tetracarboxylic dianhydride component of the specific diamine. The molecular weight of the polymer contained in the liquid crystal alignment agent of the present invention is considered to be derived therefrom. The weight average molecular weight measured by the GPC (gel permeation chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000, in terms of film coating strength, workability at the time of coating film formation, uniformity of coating film, and the like. The organic solvent used in the liquid crystal alignment agent of the invention is not particularly limited as long as it is an organic solvent capable of dissolving the above resin component. The organic solvent may be an organic solvent or a mixed solvent of two or more kinds. Specific examples of the solvent of the -24-201202176 machine can be exemplified by the organic solvent exemplified in the above polyamic acid synthesis. Among them, from the viewpoint of solubility of the resin, N.methyl-2-pyrrolidone, τ-butyrolactone, N-ethyl-2-pyrrolidone, and 1,3 -dimethyl-2-imidazolidinone are preferred. And 3-methoxy-N,N-dimethylpropanamide. Further, the solvent shown below is preferably used in a solvent having a high melting property of a resin component because it can improve the uniformity of the uniformity of the coating film. For example, isopropanol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl 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 monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, two Propylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, two Isopropyl ether, ethyl isopropyl ether, diisobutylene, amyl acetate, butyl butyrate, dibutyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n-Heptane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methyl Methyl oxypropionate 3-ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxy Propyl propionate, butyl methoxypropionate-25- 201202176, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy:, 1-benzene Oxy-2-propanol, propylene glycol monoacetate, propylene glycol, propylene glycol-1-monomethyl ether-2-acetate, butanediol-1-monoethyl ether, dipropylene glycol, 2-(2-ethoxyl) Propoxy)propanol, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl-1-hexyl lactate, and the like. When the organic solvent is used in a mixture of a plurality of solvents, it is preferably a total of 20% to 60% by mass of the solvent contained in the liquid crystal alignment agent. The liquid crystal alignment agent of the present invention may contain, for example, a compound which improves the uniformity of the film thickness when the liquid crystal alignment agent is applied, and which improves the adhesion between the liquid crystal alignment film and the substrate. The film thickness uniformity or the surface composition of the liquid crystal alignment film is exemplified by a fluorine-based surfactant, a rhodium-based surfactant-based surfactant, and the like. More specifically, examples are EF301, EF3 03, and EF3 52 (TOKEMU PRODUCTS, MEGAFAC F171, F173, R-30 (Greater Japan Ink FLUORAD FC430, FC43 1 (manufactured by Sumitomo 3M), GUARD AG710, SUNFLON S- 3, SC 101, SC103, SC104, SC105, and SC106 (when the surfactant is used by Asahi Glass Co., Ltd., the use ratio thereof is preferably 0.01 to 2 parts by mass per 100 parts by mass of the resin component contained in the liquid crystal. 1 part by mass. As for the adhesion of the liquid crystal alignment film to the substrate, the compound 2-propanol diacetate-2-acetate methyl ester, lactate, 2-ethyl is used. The 5 to 80 mass fraction is used. As a combination of sex and surface properties, non-ionic EF TOP system, system, ASHAHI SC102, and so on. In the case of a specific agent, the specific example is -26-201202176, and examples thereof include a functional decane compound and an epoxy group-containing compound, for example, 3-aminopropyltrimethoxydecane, 3-amino group. Propyl sand, 2-aminopropyltrimethoxy sand, 2-aminopropyl decane, N-(2-aminoethyl)-3-aminopropyltrimethoxy (2-amino) Ethyl)-3-aminopropylmethyldimethoxydecane, methoxytrimethoxydecane, 3-ureidopropyltriethoxydecane, -3-aminopropyltrimethoxydecane, N - ethoxycarbonyl-3-amine ethoxy decane, N-triethoxydecyl propyl tris-ethyltriamine oxy decyl propyl tris-ethyltriamine, 10-trimethoxy oxime triazole Decane, 10-triethoxy-1,4,7-triazadecane, decylalkyl-3,6-diazaindolyl acetate, 9-triethoxyphosphonium diazepine Acetate, N-benzyl-3-aminopropyltrimethoxy N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-amine methoxydecane, N- Phenyl-3-aminopropyltriethoxydecaneoxyethyl)-3-aminopropyltrimethoxydecane, N-bis( )-3-aminopropyltriethoxy Base decane, ethylene glycol diglycidyl glycol diglycidyl ether, propylene glycol diglycidyl ether, triglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol oleyl ether, 1,6-hexanediol Glycidyl ether, glycerol dihydrate 2.2- dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetrakis-2,4-hexanediol, N,N,N',N '-Tetraglycidyl-M-1.3-bis (Ν,Ν·diglycidylaminomethyl) ring 1^ small, :^',:^'-tetraglycidyl-4,4'- Diaminodiphenylformamidine-allyl-indole-glycidyl)aminopropyltrimethoxy ruthenium and the like. Triethoxy ethoxy methoxy decane, hydrazine-3 ureido propyl hydrazine - ethoxycarbonyl propyl trisole: ΝΝtrimethyl-1,4,7-9-trimethoxyalkyl-3,6-ylnonane , propyl propyl, bismuth-bis (oxyethyl ether ether, polypropylene glycol diglycidyl ether, glycidyl phenyl diamine, I hexane, alkane, 3-(alkane, 3-( -27- 201202176) N,N-diglycidyl)aminopropyltrimethoxydecane, etc. Further, in order to further improve the friction resistance of the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention, 2,2'-bis ( a phenolic compound such as 4-hydroxy-3,5-dihydroxymethylphenyl)propane or tetrakis(methoxyethyl)bisphenol. When these compounds are used, the resin component contained in the liquid crystal alignment agent is 1 〇. The amount of the yttrium is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass. The liquid crystal alignment agent of the present invention may be added to the liquid crystal alignment agent in addition to the above, without damaging the effects of the present invention. A dielectric or conductive substance that changes the dielectric properties or electrical conductivity of the liquid crystal alignment film. <Liquid alignment film/liquid crystal display element> The obtained liquid crystal alignment agent of the present invention can be applied to a substrate, dried, and fired to form a film. The film surface can be used as a liquid crystal alignment film by alignment treatment such as rubbing. The transparent substrate is not particularly limited, and for example, a glass substrate or the like can be used. Further, in the reflective liquid crystal display device, an opaque film such as a germanium wafer can be used only in a single-sided substrate. A material for reflecting light such as aluminum is used. Examples of the coating method of the liquid crystal alignment agent include a spin coating method, a printing method, an inkjet method, etc. Further, the liquid crystal alignment agent is preferably a film having a pore diameter of 0.1 μm to 1 μm. The filter is filtered and then coated. The drying step after coating the liquid crystal alignment agent may be necessary or unnecessary, but the time from the application to the end of the burning is not necessarily for each substrate, or coating In the case where the cloth is not immediately fired, it is preferred to include a drying step. The drying is carried out by evaporating the solvent to such an extent that the shape of the coating film is not changed by transfer of a substrate or the like. The means is not particularly limited. For the specific example, it is exemplified by a hot plate at 50 to 150 ° C, preferably 80 to 120 ° C, and dried for 0.5 to 30 minutes, preferably 1 to 5 The method of applying the liquid crystal alignment agent may be carried out at any temperature of 100 to 350 ° C, preferably 120 ° C to 300 ° C, more preferably 150 ° C to 250 °. C. The firing can be carried out by a hot plate, a hot air circulating furnace, an infrared furnace, etc. The thickness of the film after firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 1 nm. The material of the rubbing cloth used for the treatment may, for example, be cotton, nylon, or the like. In the liquid crystal display device of the present invention, a substrate to which a liquid crystal alignment film is attached 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 known method as a liquid crystal display element. For example, one example of the liquid crystal cell formation is to prepare a pair of substrates for forming a liquid crystal alignment film, and to spread a spacer on the liquid crystal alignment film of the single substrate so that the liquid crystal alignment film surface is inside. A substrate, a method of injecting a liquid crystal into a vacuum and encapsulating it, 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 packaged. The spacer thickness at this time is preferably from 1 to 30 μm, more preferably from 2 to ΙΟμη. The present invention will be described in more detail by way of the following examples, but the invention is not limited thereto. Example -29-201202176 (Example 1) Synthesis of 2,4-dinitro-1-(4-vinyloxy)butoxybenzene [Chemical 8]
Et3N(1.1 eq) 甲苯，100°CEt3N (1.1 eq) toluene, 100 ° C
.Λ 於5 OOmL (毫升）三頸燒瓶內，添加四亞甲基二醇單 乙烯醚5.94g、三乙胺5.70g及甲苯30mL。接著，將系統內 加熱至l〇〇°C，滴加溶解於20mL甲苯中之2,4-二硝基氟苯 10g，於loot攪拌6小時。反應結束後，添加純水50mL， 攪拌後，添加乙酸乙酯萃取有機層。於有機層中添加無水 硫酸鎂予以脫水乾燥，過濾後，使用旋轉蒸發器進行溶劑 餾除。殘留物使用乙酸乙酯/己烷=7/3 (體積比，以下同 )之混合溶劑進行再結晶，獲得13.2g目的物（收率90%) 。目的物之1H-NMR測定結果顯示如下。由該結果，確認 所得固體爲目的之二硝基化合物。且所謂1H-NMR意指分 子內氫原子之核磁共振光譜。 'HNMR ( 400MHz,CDCla ) : δ = 8.75 ( s,lH) , 8.40-8.45 ( d,lH) ,7.18-7.21 ( d,lH) ,6.43-6.45 (m,lH) ,4.27-4.31 (t,2H) ,4.16-4.22 (d,lH) ,4.00-4.03(d,lH) ,3.75 -3.79 ( t,2H ) , 1.9 8 - 2.0 7 ( m, 1 H ) ,1.88-1.94 ( m, 1 H ) 〇 -30- 201202176 [化9] o2nΛ In a 500 mL (ml) three-necked flask, 5.94 g of tetramethylene glycol monovinyl ether, 5.70 g of triethylamine, and 30 mL of toluene were added. Next, the inside of the system was heated to 10 ° C, 10 g of 2,4-dinitrofluorobenzene dissolved in 20 mL of toluene was added dropwise, and the mixture was stirred for 6 hours at the loot. After completion of the reaction, 50 mL of pure water was added, and after stirring, the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer to dehydrate and dry, and after filtration, solvent distillation was carried out using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate / hexane = 7 / 3 (volume ratio, ss.) to obtain 13.2 g of the object (yield: 90%). The results of 1H-NMR measurement of the target showed the following. From the results, it was confirmed that the obtained solid was the intended dinitro compound. The so-called 1H-NMR means a nuclear magnetic resonance spectrum of a hydrogen atom in a molecule. 'HNMR (400MHz, CDCla) : δ = 8.75 ( s,lH) , 8.40-8.45 ( d,lH) , 7.18-7.21 ( d,lH) ,6.43-6.45 (m,lH) , 4.27-4.31 (t, 2H) , 4.16-4.22 (d, lH) , 4.00-4.03 (d, lH), 3.75 - 3.79 ( t, 2H ) , 1.9 8 - 2.0 7 ( m, 1 H ) , 1.88-1.94 ( m, 1 H 〇-30- 201202176 [化9] o2n
N〇2N〇2
Fe (10 eq) 10%NH4CI aq. (20 eq) 甲苯，70 eC，2.5 hFe (10 eq) 10%NH4CI aq. (20 eq) toluene, 70 eC, 2.5 h
於500mL三頸燒瓶內，添加上述之二硝基化合物2.12g 、甲苯20mL及10質量％氯化銨水溶液80mL。接著，將系 統內加熱至70°C，添加鐵（電解鐵）4.2g，於70°C攪拌 2.5小時。反應結束後，添加飽和碳酸氫鈉水溶液30mL， 過濾沉澱物，以甲苯洗淨。以乙酸乙酯萃取濾液，於有機 層中添加無水硫酸鎂予以脫水乾燥，過濾後’使用旋轉蒸 發器進行溶劑餾除。殘留物使用乙酸乙酯/己烷=7/3之混 合溶劑進行再結晶，獲得〇 . 5 9 g目的物（收率3 8 % )。目的 物之1H-NMR測定結果顯示如下。由該結果’確認所得固 體爲目的之二胺化合物。 JHNMR ( 400MHz,CDC13 ) ： <5 = 6.60-6.62 ( d,lH) ,6.44-6.51 ( m,lH) ,6.13-6.14 ( d,lH) ,6.03-6.07 ( m,lH) ,4.14-4.21 ( d,lH) ,3.96-4.00 ( d,lH ),3.92-3.96 ( t,2H ) ,3.73-3.73 ( m,4H) ,3.34 ( s,2H ) 1 .85 - 1 .87 ( m，4H )。 (實施例2 ) 十一碳-10 -嫌基-3,5 -二硝基苯甲酸醋之1=1成 -31 - 201202176 [化 ίο]Into a 500 mL three-necked flask, 2.12 g of the above dinitro compound, 20 mL of toluene, and 80 mL of a 10% by mass aqueous ammonium chloride solution were added. Next, the inside of the system was heated to 70 ° C, and 4.2 g of iron (electrolytic iron) was added, and the mixture was stirred at 70 ° C for 2.5 hours. After completion of the reaction, 30 mL of a saturated aqueous sodium hydrogencarbonate solution was added, and the precipitate was filtered and washed with toluene. The filtrate was extracted with ethyl acetate, and dried over anhydrous sodium sulfate (MgSO4), and then filtered and evaporated. The residue was recrystallized using a mixed solvent of ethyl acetate / hexane = 7 / 3 to give EtOAc (yield: 38%). The results of 1H-NMR measurement of the target showed the following. From the results, it was confirmed that the obtained solid is a diamine compound for the purpose. JHNMR (400MHz, CDC13): <5 = 6.60-6.62 ( d,lH) , 6.44 - 6.51 ( m,lH) , 6.13 - 6.14 ( d,lH) , 6.03-6.07 ( m,lH) ,4.14-4.21 ( d,lH) , 3.96-4.00 ( d,lH ),3.92-3.96 ( t,2H ) ,3.73-3.73 ( m,4H) ,3.34 ( s,2H ) 1.85 - 1 .87 ( m,4H ). (Example 2) 1 = 11 -10 -5-dinitrobenzoic acid vinegar 1 = 1 to -31 - 201202176 [Chemical]
於300mL三頸燒瓶中，添加10-十一碳烯-1-醇5.11g、 吡啶2.3 7g及四氫呋喃100mL。接著，以冰將系統內冷卻至 (TC，添加3，5 ·二硝基苯甲醯氯8.3 g，在室溫攪拌2小時。 反應結束後，添加純水20 mL，攪拌後，添加乙酸乙酯萃 取有機層。於有機層中添加無水硫酸鎂予以脫水乾燥，過 濾後，使用旋轉蒸發器進行溶劑餾除。殘留物使用乙酸乙 酯/己烷=7/3之混合溶劑進行再結晶，獲得6.9g目的物（收 率63% )。目的物之1H-NMR測定結果顯示如下。由該結 果，確認所得固體爲目的之二硝基化合物。 !HNMR ( 400MHz,[D6]-DMSO ) : (5 = 9.04 ( s,lH) 8.90 ( s,2H ) ,5.73-5.83 ( m,lH) ,4.90-5.00 (m,2H ) ,4.38-4.41 ( t,2H) ,1.97-2.03 ( m,2H) ,1.73- 1.80 ( t}2H) ,1.2 8- 1.45 ( m,12H)。 十一碳-10-烯基-3，5-二胺基苯甲酸酯之合成 -32- 201202176 [化 11]To a 300 mL three-necked flask, 5.11 g of 10-undecen-1-ol, 2.3 g of pyridine, and 100 mL of tetrahydrofuran were added. Next, the system was cooled to (TC, 8.3 g of 3,5-dinitrobenzidine chloride, and stirred at room temperature for 2 hours. After the reaction was completed, 20 mL of pure water was added, and after stirring, acetic acid B was added. The organic layer was extracted with an ester, and anhydrous sodium sulfate was added to the organic layer to dehydrate and dry, and after filtration, the solvent was distilled off using a rotary evaporator, and the residue was recrystallized using a mixed solvent of ethyl acetate / hexane = 7 / 3 to obtain 6.9 g of the object (yield: 63%). The result of 1H-NMR measurement of the object of the object was as follows. From the result, it was confirmed that the obtained solid was the intended dinitro compound. HNMR (400 MHz, [D6]-DMSO) : 5 = 9.04 ( s, lH) 8.90 ( s, 2H ) , 5.73-5.83 ( m, lH) , 4.90-5.00 (m, 2H ) , 4.38-4.41 ( t, 2H) , 1.97-2.03 ( m, 2H) , 1.73- 1.80 (t}2H), 1.2 8- 1.45 (m,12H). Synthesis of undec-10-enyl-3,5-diaminobenzoate-32- 201202176 [Chem.11]
於300mL三頸燒瓶中，添加上述之二硝基化合物6.55g 、四氫呋喃50mL及純水50mL，使系統內攪拌’添加氯化 錫17.06g，在60°C攪拌2小時。反應結束後，添加5質量％ 碳酸氫鈉400ml，使pH成爲7-8。其後’添加乙酸乙酯 16 0ml，利用過濾濾除白色沉澱物，有機層以乙酸乙酯萃 取。於有機層中添加無水硫酸鎂予以脫水乾燥，過濾後， 使用旋轉蒸發器進行溶劑餾除。殘留物使用乙酸乙酯/己 烷=7/3之混合溶劑進行再結晶，獲得4.5g目的物（收率 82% )。目的物之1H-NMR測定結果顯示如下。由該結果 ，確認所得固體爲目的之二胺化合物。 !HNMR ( 400MHz,[D6]-DMSO ) ：δ = 6.41 ( s,2H) 6.01 ( s,lH) ,5.73 -5.84 ( m,lH) ,4.91-5.01 (m,6H ) ,4.13-4.16 ( t,2H) ,1.98 -2.0 2 ( m,2H) ,1.60- 1.67 ( m，2H) ,1.27- 1.3 7 ( m，12H)。 以下實施例及比較例中之化合物代號如下。 -33- 201202176 <四羧酸二酐> CBDA : 1，2,3,4-環丁烷四羧酸二酐 [化 12]To a 300 mL three-necked flask, 6.55 g of the above-mentioned dinitro compound, 50 mL of tetrahydrofuran, and 50 mL of pure water were added, and 17.06 g of tin chloride was added to the system while stirring, and the mixture was stirred at 60 ° C for 2 hours. After completion of the reaction, 400 ml of 5 mass% sodium hydrogencarbonate was added to adjust the pH to 7-8. Thereafter, 16 ml of ethyl acetate was added, and the white precipitate was filtered, and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer to dehydrate and dry, and after filtration, solvent distillation was carried out using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate / hexane = 7 / 3 to obtain 4.5 g of object (yield: 82%). The results of 1H-NMR measurement of the target showed the following. From the results, it was confirmed that the obtained solid was the intended diamine compound. !HNMR ( 400MHz, [D6]-DMSO ) : δ = 6.41 ( s, 2H) 6.01 ( s,lH) , 5.73 -5.84 ( m,lH) ,4.91-5.01 (m,6H ) ,4.13-4.16 ( t , 2H), 1.98 -2.0 2 (m, 2H), 1.60- 1.67 (m, 2H), 1.27-1.3 7 (m, 12H). The compound numbers in the following examples and comparative examples are as follows. -33- 201202176 <tetracarboxylic dianhydride> CBDA : 1,2,3,4-cyclobutane tetracarboxylic dianhydride [Chemical 12]
<二胺> DAC-1: 4-(4-(乙烯氧基）丁氧基）苯-1,3-二胺 DAC-2:十一碳-10-烯基-3,5-二胺基苯甲酸酯 DA-1: 2-(甲基丙烯醯氧基）乙基-3,5-二胺基苯甲 酸酯 DA-2: 1，3-二胺基苯 [化 13]<Diamine> DAC-1: 4-(4-(vinyloxy)butoxy)benzene-1,3-diamine DAC-2: undecyl-10-alkenyl-3,5-di Aminobenzoate DA-1: 2-(methacryloxy)ethyl-3,5-diaminobenzoate DA-2: 1,3-diaminobenzene [Chemical 13]
H2NH2N
o nh2 H# 人ΆνΗ2 DAC-1 DAC-2o nh2 H# 人ΆνΗ2 DAC-1 DAC-2
<有機溶劑> NMP : N-甲基-2-吡略烷酮 BC : 丁基溶纖素 -34- 201202176 (實施例3 ) 使用CBDA 7.68g( 0.03 9mol)作爲四羧酸二酐成分， 使用 DAC-1 8.89g ( 0.040mol )作爲二胺成分，於 NMP 93.94g中，在室溫反應16小時，獲得聚醯胺酸（PAA-1 ) 濃度爲15質量％之溶液。使用NMPlO.Og及BC 5.0g稀釋該 溶液lO.Og，獲得聚醯胺酸（PAA-1 )爲6質量％，NMP爲 74質量％及BC爲20質量％之液晶配向劑。 (實施例4 ) 使用CBDA 7.68g ( 0.0 3 9mol )作爲四羧酸二酐成分， 使用 DAC-2 12.17g( 0.040mol)作爲二胺成分，於 NMP 112.48g中，在室溫反應16小時，獲得聚醯胺酸（PAA-2 ) 濃度爲15質量％之溶液。使用NMPlO.Og及BC 5.0g稀釋該 溶液l〇.〇g，獲得聚醯胺酸（PAA-2)爲6質量％，NMP爲 74質量％及BC爲20質量％之液晶配向劑。 (比較例1 ) 使用CBDA 7.68g( 0.039mol)作爲四羧酸二酐成分， 使用 DA-1 10.57g ( 0.040mol )作爲二胺成分，於 NMP 103.41g中，在室溫反應16小時，獲得聚醯胺酸（PAA-3 ) 濃度爲15質量％之溶液。使用NMPlO.Og及BC 5.0g稀釋該 溶液l〇.〇g，獲得聚醯胺酸（PAA-3 )爲6質量％，NMP爲 74質量％及BC爲20質量％之作爲比較對象之液晶配向劑。 -35- 201202176 (比較例2 ) 使用CBDA 7.68g ( 0.0 3 9mol)作爲四殘酸二酐成分， 使用DA-2 4.32g ( 0.040mol )作爲二胺成分，於NMP 103.4lg中，在室溫反應16小時，獲得聚醯胺酸（PAA-4) 濃度爲15質量％之溶液。使用NMPlO.Og及BC 5.0g稀釋該 溶液lO.Og，獲得聚醯胺酸（PAA-4)爲6質量％，NMP爲 74質量％及BC爲2 0質量％之作爲比較對象之液晶配向劑。 <聚醯胺酸分子量> 上述實施例及比較例所得之聚醯胺酸分子量係利用 GPC (常溫凝膠滲透層析）裝置測定，其結果使用聚乙二 醇及聚環氧乙烷利用校正線算出平均分子量。 GPC 裝置：Shodex公司製（GPC-101 ) 管柱：Shodex公司製（KD803及KD805串聯）<Organic solvent> NMP : N-methyl-2-pyrrolidone BC : butyl celloside-34 - 201202176 (Example 3) 7.68 g (0.03 9 mol) of CBDA was used as a tetracarboxylic dianhydride component, and used. 8.89 g (0.040 mol) of DAC-1 was reacted as a diamine component in 93.94 g of NMP at room temperature for 16 hours to obtain a solution having a polyamine acid (PAA-1) concentration of 15% by mass. The solution was diluted with 10% by weight of NMP10.Og and BC 5.0g to obtain a liquid crystal alignment agent having a polyamic acid (PAA-1) of 6 mass%, NMP of 74 mass%, and BC of 20 mass%. (Example 4) Using 7.68 g (0.03 9 mol) of CBDA as a tetracarboxylic dianhydride component, 12.17 g (0.040 mol) of DAC-2 was used as a diamine component, and reacted at room temperature for 16 hours in NMP 112.48 g. A solution having a polyamine acid (PAA-2) concentration of 15% by mass was obtained. The solution was diluted with NMP10.Og and BC 5.0g to obtain a liquid crystal alignment agent having a polyamic acid (PAA-2) of 6 mass%, an NMP of 74 mass%, and a BC of 20 mass%. (Comparative Example 1) 7.68 g (0.039 mol) of CBDA was used as a tetracarboxylic dianhydride component, and DA-1 10.57 g (0.040 mol) was used as a diamine component, and the reaction was carried out for 16 hours at room temperature in 103.41 g of NMP. A solution having a polyamine acid (PAA-3) concentration of 15% by mass. The solution was diluted with NMP10.Og and BC 5.0g to obtain a liquid crystal alignment of the comparative object of polyamine (PAA-3) of 6 mass%, NMP of 74 mass%, and BC of 20 mass%. Agent. -35-201202176 (Comparative Example 2) 7.68 g (0.03 9 mol) of CBDA was used as the component of the tetrahydro acid dianhydride, and 4.32 g (0.040 mol) of DA-2 was used as the diamine component in NMP 103.4 g at room temperature. After reacting for 16 hours, a solution having a polyamine acid (PAA-4) concentration of 15% by mass was obtained. The solution was diluted with 10% by weight of NMP10.Og and BC 5.0g to obtain a liquid crystal alignment agent which is a comparative object of polyamine acid (PAA-4) of 6 mass%, NMP of 74 mass%, and BC of 20 mass%. . <Polymeric acid molecular weight> The molecular weights of the polylysine obtained in the above Examples and Comparative Examples were measured by a GPC (normal temperature gel permeation chromatography) apparatus, and as a result, polyethylene glycol and polyethylene oxide were used. The calibration line calculates the average molecular weight. GPC device: manufactured by Shodex Co., Ltd. (GPC-101) Pipe column: manufactured by Shodex (KD803 and KD805 in series)
管柱溫度：5 (TC 溶離液：N，N-二甲基甲醯胺（作爲添加劑，溴化鋰單 水合物（LiBr · H20 )爲30mmol/L，磷酸無水結晶（〇-磷 酸）爲30mmol/L及四氫呋喃（THF )爲10ml/L )。 流速：1.0ml/分鐘 校正線作成用標準樣品：TOSOH公司製TSK標準聚環 氧乙烷（分子量約 900, 〇〇〇、150,000、100, 〇〇〇、30,000) 及聚合物實驗室公司製之聚乙二醇（分子量約12，000、 4,000 ' 1,000 ) 〇 -36- 201202176 表7中顯示數平均分子量（Μη)、重量平均分子量（ Mw)及Ζ平均分子量（Μζ)之算出結果。 表 7 聚醯胺酸 Μη M w Μζ PAA-1 1 8794 76187 214741 PAA-2 23 844 97494 185982 PAA-3 2 1860 61973 107981 PAA-4 83 63 1 7878 3 1240 <液晶胞之製作> 對於實施例3、4及比較例1、2所調製之液晶配向劑如 下述般製作液晶胞。 於附有透明電極之玻璃基板上旋轉塗佈液晶配向劑， 於7〇 °C的加熱板上乾燥70秒後，於230 °C之加熱板上進行 1〇分鐘燒成，形成膜厚l〇〇nm之塗膜。對該塗膜面以輥徑 120mm之摩擦裝置使用縲縈布，以輥旋轉數lOOOrpm、輥 行進速度50mm/秒及壓入量0.3mm之條件予以摩擦，獲得 附液晶配向膜之基板。準備兩片附液晶配向膜之基板，於 其一片之液晶配向膜面上，散佈6μιη間隔物後，於其上印 刷密封劑，將另一片基板以液晶配向膜面對向且摩擦方向 直行之方式予以貼合後，使密封劑硬化製作空的液晶胞。 於該空的液晶胞中藉減壓注入法，注入液晶MLC-20 03 ( Merck公司製），封住注入口，獲得扭轉向列型液晶胞。 <電壓保持率之評價> -37- 201202176 將以上述記載之方法製作之扭轉向列型液晶胞在90°C 的溫度下施加60ps之4V電壓，測定167ms後之電壓，由下 述式求出能保持多少電壓作爲電壓保持率（％)。且，電 壓保持率之測定係利用東陽技術公司製之VHR· 1電壓保持 率測定裝置。又，V1 :施加電壓（V ) ，V2 :極性反轉電 壓（V )。Column temperature: 5 (TC dissolving solution: N,N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr · H20) is 30 mmol/L, and anhydrous phosphate crystals (〇-phosphoric acid) is 30 mmol/L) And tetrahydrofuran (THF) was 10 ml/L. Flow rate: 1.0 ml/min Calibration line for standard preparation: TSK standard polyethylene oxide manufactured by TOSOH Co., Ltd. (molecular weight: about 900, 〇〇〇, 150,000, 100, 〇〇〇 , 30,000) and Polyethylene Glycol (Polymer Molecular Weight: 12,000, 4,000 '1,000) 〇-36- 201202176 Table 7 shows the number average molecular weight (Μη), weight average molecular weight (Mw) and Ζ The calculation results of the average molecular weight (Μζ). Table 7 Polyphosphonium Μ M w Μζ PAA-1 1 8794 76187 214741 PAA-2 23 844 97494 185982 PAA-3 2 1860 61973 107981 PAA-4 83 63 1 7878 3 1240 < [Production of Liquid Crystal Celles] The liquid crystal cells were prepared as follows for the liquid crystal alignment agents prepared in Examples 3 and 4 and Comparative Examples 1 and 2. The liquid crystal alignment agent was spin-coated on the glass substrate with the transparent electrode, at 7 After heating for 70 seconds on a hot plate of 〇°C, heating plate at 230 °C The film was fired for 1 minute to form a coating film having a film thickness of 10 nm. The coating film was rubbed with a roll diameter of 120 mm, and the roll was rotated at 1000 rpm, the roll travel speed was 50 mm/sec, and pressed. Rubbing the substrate with a dose of 0.3 mm to obtain a substrate with a liquid crystal alignment film. Prepare two substrates with a liquid crystal alignment film, and spread a 6 μm spacer on the liquid crystal alignment film surface of one of them, and then print a sealant thereon. The other substrate is bonded in such a manner that the liquid crystal alignment film faces and rubs in a straight direction, and then the sealant is hardened to form an empty liquid crystal cell. The liquid crystal cell is injected into the liquid crystal cell by a reduced pressure injection method, and the liquid crystal MLC-20 03 is injected. (manufactured by Merck Co., Ltd.), the injection port was sealed to obtain a twisted nematic liquid crystal cell. <Evaluation of voltage holding ratio> -37-201202176 The twisted nematic liquid crystal cell produced by the method described above was at 90 °C. At a temperature of 4 volts of 60 ps, a voltage of 167 ms was measured, and the voltage which can be held as a voltage holding ratio (%) was determined by the following formula. The voltage holding ratio was measured by using VHR·1 manufactured by Dongyang Technology Co., Ltd. Voltage hold Rate measuring device. Further, V1: applied voltage (V), V2: polarity reversal voltage (V).
電壓保持率（％) xlOO <摩擦耐性之評價> 與上述液晶胞之製作同樣之方法製作附有液晶配向膜 之基板。此時，摩擦條件之壓入量變更爲〇.5mm而進行。 以共焦點雷射顯微鏡觀察所得液晶配向膜表面，進行下述 評價。 〇：未觀察到削減渣或摩擦傷痕 △:觀察到削減渣或摩擦傷痕 X :膜剝離或以目視觀察到摩擦傷痕 表8顯示電壓保持率與摩擦耐性之評價結果。 表 8Voltage holding ratio (%) xlOO <Evaluation of friction resistance> A substrate having a liquid crystal alignment film was produced in the same manner as in the production of the above liquid crystal cell. At this time, the amount of pressing of the friction conditions was changed to 〇5 mm. The surface of the obtained liquid crystal alignment film was observed by a confocal laser microscope, and the following evaluation was carried out. 〇: No slag or friction scar was observed. Δ: Slag or friction scar was observed. X: Film peeling or visual observation of friction scars Table 8 shows the results of evaluation of voltage holding ratio and frictional resistance. Table 8
液晶配向劑 聚合物成分 電壓保持率（％) 摩擦耐性 實施例3 PAA-1 54.5 〇 實施例4 PAA-2 77.9 〇 比較例1 PAA-3 6.2 〇 比較例2 PAA-4 18.1 X -38- 201202176 [產業上之可能利用性] 本發明之二胺化合物可利用作爲聚醯胺酸、聚醯胺酸 酯、聚醯亞胺、聚醯胺等之各種聚合物的原料。且所合成 之聚合物可利用作爲構成液晶配向膜之材料。 本發明之液晶配向劑可利用作爲液晶顯示元件之液晶 配向膜。本發明之液晶顯示元件可較好地使用於TN液晶 顯示元件、STN液晶顯示元件、TFT液晶顯示元件、AV液 晶顯示元件、IPS液晶顯示元件、OCB液晶顯示元件等之 利用各種方式之顯示元件。 又’於本文引用2010年2月26日申請之曰本特願2010-043 3 73號說明書、申請專利範圍及摘要作爲本發明說明書 之揭示，倂入本文供參考* -39-Liquid crystal alignment agent polymer component voltage retention ratio (%) Friction resistance Example 3 PAA-1 54.5 〇 Example 4 PAA-2 77.9 〇 Comparative Example 1 PAA-3 6.2 〇 Comparative Example 2 PAA-4 18.1 X -38- 201202176 [Industrial Applicability] The diamine compound of the present invention can be used as a raw material of various polymers such as polyglycolic acid, polyglycolate, polyimide, and polyamine. Further, the synthesized polymer can be utilized as a material constituting the liquid crystal alignment film. The liquid crystal alignment agent of the present invention can be used as a liquid crystal alignment film of a liquid crystal display element. The liquid crystal display element of the present invention can be preferably used in various types of display elements such as a TN liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, an AV liquid crystal display element, an IPS liquid crystal display element, and an OCB liquid crystal display element. The disclosure of Japanese Patent Application No. 2010-043357, filed on Feb. 26, 2010, the disclosure of which is hereby incorporated by reference in its entirety in
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