TW201348294A - Novel diamine, polymer, liquid crystal alignment agent, and liquid crystal alignment film, and liquid crystal display element using same - Google Patents

Novel diamine, polymer, liquid crystal alignment agent, and liquid crystal alignment film, and liquid crystal display element using same Download PDF

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TW201348294A
TW201348294A TW102103982A TW102103982A TW201348294A TW 201348294 A TW201348294 A TW 201348294A TW 102103982 A TW102103982 A TW 102103982A TW 102103982 A TW102103982 A TW 102103982A TW 201348294 A TW201348294 A TW 201348294A
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liquid crystal
acid
diamine
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crystal alignment
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TWI561555B (en
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Takahiro Noda
Oki Mochizuki
Daisuke Sakuma
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Nissan Chemical Ind Ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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    • C08G73/00Macromolecular 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
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    • C08G73/00Macromolecular 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
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    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723Polyimide, polyamide-imide

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Abstract

A polymer comprising a polyimide obtained by dewatering cyclization (imidization) of a polyamide, polyamic acid, polyamic acid ester, or the polyamic acid and/or polyamic acid ester obtained using a diamine represented by general formula [1]. (In the formula, A represents a thermally desorbable organic group; n number of NHA groups are provided (n = 1 or 2), and the NHA groups are present at the ortho position with respect to the amino groups (NH2 groups); and the amino groups are present at the meta position or the para position.)

Description

新穎二胺,聚合物,液晶配向劑,液晶配向膜,及使用其之液晶顯示元件 Novel diamine, polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the same

本發明係有關新穎二胺、液晶顯示元件所使用之液晶配向劑、液晶配向膜、及液晶顯示元件。 The present invention relates to a novel diamine, a liquid crystal alignment agent used for a liquid crystal display element, a liquid crystal alignment film, and a liquid crystal display element.

液晶顯示元件中,液晶配向膜之角色為使液晶配向於一定方向。目前工業上所使用之主要液晶配向膜係由,將由聚醯亞胺先驅物之聚醯胺酸(polyamide acid)(也稱為polyamic acid)及聚醯亞胺之溶液所形成的聚醯亞胺系之液晶配向劑,塗佈於基板上成膜所得。又,相對於基板面使液晶平行配向或傾斜配向時,成膜後係另藉由摩擦進行表面延伸處理。又,曾提案以利用藉由照射偏光紫外線等之各向異性光學反應的方法取代摩擦處理,且近年來朝向工業化進行檢討。 In the liquid crystal display device, the role of the liquid crystal alignment film is to align the liquid crystal in a certain direction. The main liquid crystal alignment film currently used in the industry consists of a polyimine formed from a solution of polyaminic acid precursor (polyamic acid) and polyimine. A liquid crystal alignment agent is applied to a substrate to form a film. Further, when the liquid crystal is aligned in parallel or obliquely with respect to the substrate surface, the surface extension treatment is performed by friction after film formation. In addition, it has been proposed to replace the rubbing treatment by a method of irradiating an anisotropic optical reaction such as polarized ultraviolet light, and in recent years, it has been reviewed for industrialization.

為了提升液晶顯示元件之顯示特性,曾提案藉由各種變更聚醯胺酸及聚醯亞胺之構造而進行最適化,或摻雜特性不同之樹脂,或添加添加劑等,可改善液晶配向性及改善預傾角之控制性、電特性等,且進一步改善顯示特性各種技術。例如為了得到高電壓保持率,曾提案使 用具有特定之重覆構造的聚醯亞胺樹脂(參考專利文獻1等)。又,曾提案藉由相對於殘像顯像,使用除了醯亞胺基以外具有氮原子的可溶性聚醯亞胺,而縮短至殘像消失之時間(參考專利文獻2等)。 In order to improve the display characteristics of the liquid crystal display device, it has been proposed to optimize the liquid crystal alignment property by optimizing various structures of polyamic acid and polyimine, or by using a resin having different doping characteristics or adding an additive. Various techniques for improving the controllability, electrical characteristics, and the like of the pretilt angle and further improving the display characteristics. For example, in order to obtain a high voltage holding ratio, it has been proposed to make A polyimide resin having a specific repetitive structure is used (refer to Patent Document 1, etc.). In addition, it has been proposed to shorten the time until the afterimage disappears by using a soluble polyimine having a nitrogen atom other than the quinone imine group for image development (see Patent Document 2).

但隨著液晶顯示元件之高性能化、大面積化、顯示裝置之省電化為趨勢,及適用於各種環境之條件下,要求液晶配向膜之特性更趨嚴苛。特別是將液晶配向劑塗佈於基板時,會有拉長接觸時間時因析出或分離而發生印刷不良,及長期使用液晶顯示元件時會增加離子密度,及因蓄積電荷而烙印等問題之課題,但先前之技術難同時解決兩者。 However, with the trend of high performance, large area of the liquid crystal display element, power saving of the display device, and application to various environments, the characteristics of the liquid crystal alignment film are required to be more severe. In particular, when a liquid crystal alignment agent is applied to a substrate, printing defects occur due to precipitation or separation during an extended contact time, and ion density is increased when a liquid crystal display element is used for a long period of time, and problems such as branding due to accumulation of charges are caused. However, the previous technology is difficult to solve both at the same time.

因此曾提案,使用含有被t-丁氧基羰基(以下稱為Boc基)保護之烷基胺的二胺之液晶配向劑(參考專利文獻3)。該技術為,形成具有被Boc基保護之1級或2級脂肪族胺的聚醯亞胺先驅物或聚醯亞胺之塗膜後,焙燒時會生成反應性較高之1級或2級脂肪族胺進行分子間交聯反應,而生成機械強度優良之聚醯亞胺膜。 Therefore, it has been proposed to use a liquid crystal alignment agent containing a diamine of an alkylamine protected by a t-butoxycarbonyl group (hereinafter referred to as a Boc group) (refer to Patent Document 3). The technique is to form a coating film of a polyimine precursor or a polyimine having a Boc group-protected primary or secondary aliphatic amine, and then generate a higher reactivity level 1 or 2 when calcined. The aliphatic amine undergoes an intermolecular crosslinking reaction to form a polyimide film having excellent mechanical strength.

該聚醯亞胺膜雖可提升耐摩擦性,但會有逆相降低液晶配向性,也易蓄積RDC(殘留DC電壓)之課題。 Although the polyimide film can improve the rubbing resistance, it has a problem that the reverse phase reduces the liquid crystal alignment property and the RDC (residual DC voltage) is easily accumulated.

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1:特開平2-287324號公報 Patent Document 1: JP-A-2-287324

專利文獻2:特開平10-104633號公報 Patent Document 2: Japanese Patent Publication No. Hei 10-104633

專利文獻3:WO 2006-126555號公報 Patent Document 3: WO 2006-126555

發明之概要 Summary of invention

有鑑於上述事情,本發明之目的為,提供相對於基板具有良好印刷性之液晶配向劑,及具有優良耐摩擦性與液晶之配向性,難蓄積RDC,且既使經長期高溫、高濕試驗或照射背光也難降低液晶顯示元件特性之液晶配向膜。即,提供可得具有該類特性之聚醯胺、聚醯亞胺先驅物、聚醯亞胺之二胺,另外係提供,使用其之液晶配向劑,及降低對比及不易烙印之液晶顯示元件。 In view of the above, an object of the present invention is to provide a liquid crystal alignment agent having good printability with respect to a substrate, and having excellent rubbing resistance and alignment of liquid crystal, and it is difficult to accumulate RDC, and even after long-term high temperature and high humidity test Or a liquid crystal alignment film which is difficult to reduce the characteristics of a liquid crystal display element by irradiating a backlight. That is, a polyamine capable of obtaining such a property, a polyimine precursor, a polyamine of a polyimine, and a liquid crystal alignment agent using the same, and a liquid crystal display element having reduced contrast and less imprinting are provided. .

本發明係有鑑於上述事情之發明,其課題為提供具有液晶配向劑之印刷性(聚合物相對於溶劑之溶解性)、耐摩擦性優良且液晶之配向性良好,不易蓄積RDC,既使長時間高溫環境下或背光等之光照射狀況下仍不易降低電壓保持率之該液晶配向膜的液晶顯示元件,及形成該液晶配向膜用之液晶配向劑。 The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a liquid crystal alignment agent having printability (solubility of a polymer with respect to a solvent), excellent rub resistance, and good liquid crystal alignment property, and it is difficult to accumulate RDC. A liquid crystal display element of the liquid crystal alignment film in which the voltage holding ratio is not easily lowered under a high-temperature environment or a light irradiation condition such as a backlight, and a liquid crystal alignment agent for forming the liquid crystal alignment film.

經本發明者專心研究後發現,含有所使用之二胺成分為含有藉由加熱而生成胺基之官能基的二胺化合物(以下也稱為特定二胺化合物)之聚醯胺、聚醯胺酸,及/ 或該聚醯胺酸醯亞胺化所得之聚醯亞胺的液晶配向劑可極有效達成上述目的,而完成本發明。又,上述特定之二胺化合物為,含有文獻未曾記載之新穎化合物之物。 As a result of intensive studies by the present inventors, it has been found that a diamine compound (hereinafter also referred to as a specific diamine compound) containing a diamine component (hereinafter also referred to as a specific diamine compound) containing a functional group which generates an amine group by heating is used. ,and/ Or the liquid crystal alignment agent of the polyimine obtained by imidization of the polyphosphonium amide can be extremely effective in achieving the above object, and the present invention has been completed. Further, the specific diamine compound described above contains a novel compound not described in the literature.

即,本發明為具有下述要旨之發明。 That is, the present invention is an invention having the following gist.

1.一種聚合物,其為由使用下述式[1]所表示之二胺所得的聚醯胺、聚醯胺酸、聚醯胺酸酯,或該聚醯胺酸及/或聚醯胺酸酯脫水閉環(醯亞胺化)所得之聚醯亞胺所形成。 A polymer obtained by using a diamine represented by the following formula [1], a polyamido acid, a polyamidomate, or the polyamic acid and/or polyamine The polyester imine obtained by the ester dehydration ring closure (oxime imidization) is formed.

(式中A表示可藉由熱而脫離所得之有機基。NHA基為具備n個(n=1或2),且相對於胺基(NH2基)存在位於鄰位。又,胺基相互間存在位於間位或對位)。 (wherein A represents an organic group which can be removed by heat. The NHA group has n (n = 1 or 2) and is ortho-position relative to the amine group (NH 2 group). Further, the amine groups are mutually There is a meta or meta position.

又以NHA基為1個為佳,此時係以下述式1a表示。 Further, it is preferable that one NHA group is used, and in this case, it is represented by the following formula 1a.

2.式[1]中,有機基A較佳為tert-丁氧基羰基。 2. In the formula [1], the organic group A is preferably a tert-butoxycarbonyl group.

3.一種聚合物,其為由特徵係含有5至95mol%之一般式[1]或[1a]記載之二胺的聚醯胺、聚醯胺酸、聚醯胺酸酯,或將該聚醯胺酸及/或聚醯胺酸酯脫水閉環(醯亞胺化)所得之聚醯亞胺所形成。 A polymer which is a polyamine, a polyglycolic acid, a polyamidite ester characterized by containing 5 to 95 mol% of the diamine of the general formula [1] or [1a], or the poly It is formed by the polyimine obtained by dehydration ring closure of lysine and/or polyamidolate.

一種聚合物,其為由特徵係含有5至50mol%之含有下述式[2]所表示之支鏈的二胺,如1至3中任何一項記載之聚醯胺、聚醯胺酸、聚醯胺酸酯,或將該聚醯胺酸及/或聚醯胺酸酯脫水閉環(醯亞胺化)所得之聚醯亞胺所形成。 A polymer comprising 5 to 50 mol% of a diamine having a branch represented by the following formula [2], wherein the polyamine, polylysine, or any one of the groups 1 to 3, The polyamidate or the polyimine obtained by dehydration (polyimidation) of the polyamic acid and/or polyphthalate is formed.

(式中,R1表示單鍵、二價之有機基,X1、X2、X3各自獨立表示苯環或環己烷環,p、q、r各自獨立表示0或1之整數,R2表示氫原子、碳數1至22之烷基或具有巢類骨架之碳數12至25之2價有機基)。 (wherein R 1 represents a single bond or a divalent organic group, and X 1 , X 2 and X 3 each independently represent a benzene ring or a cyclohexane ring, and p, q and r each independently represent an integer of 0 or 1, R 2 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or a divalent organic group having 12 to 25 carbon atoms having a nest skeleton.

5.一種液晶配向劑,其特徵為含有如1至4中任何一項所記載之聚合物(polymer)。 A liquid crystal alignment agent characterized by containing the polymer as described in any one of 1 to 4.

6.一種液晶配向膜,其為使用如5記載之液晶配向劑。 A liquid crystal alignment film which uses the liquid crystal alignment agent as described in 5.

7.一種液晶顯示元件,其為具備如6記載之液晶配向膜。 A liquid crystal display element comprising the liquid crystal alignment film according to 6.

8.一種二胺化合物,其為下述一般式[1-5]或[1-6]所表示。 A diamine compound represented by the following general formula [1-5] or [1-6].

本發明之液晶配向劑為,含有使用特定構造之二胺化合物的聚合物,因此可得良好印刷性(聚合物相對於溶劑之溶解性)。又,由本發明之液晶配向劑所得的液晶配向膜為,焙燒塗膜時會使來自特定構造之二胺化合物因脫離保護基所得之胺基反應而形成環化構造,因此可得優良耐摩擦性及良好的液晶之配向性,且難蓄積RDC,既使長時間於高溫環境下或背光等之光照射狀況下仍不易降低電壓保持率,又,可提供具有該類液晶配向膜之液晶顯示元件。 Since the liquid crystal alignment agent of the present invention contains a polymer using a diamine compound having a specific structure, good printability (solubility of a polymer with respect to a solvent) can be obtained. Further, in the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention, when the coating film is fired, the diamine compound derived from a specific structure is reacted with an amine group derived from a protective group to form a cyclized structure, thereby obtaining excellent rubbing resistance. And good alignment of the liquid crystal, and it is difficult to accumulate RDC, and it is difficult to reduce the voltage holding ratio even under a high temperature environment or a light irradiation condition such as a backlight, and a liquid crystal display element having such a liquid crystal alignment film can be provided. .

實施發明之形態 Form of implementing the invention

本發明中可將藉由含有特定二胺化合物之二胺成分與四羧酸二酐反應所得之聚醯胺酸,及該聚醯胺酸脫水閉環所得之聚醯亞胺總稱為聚合物。 In the present invention, the polyamic acid obtained by reacting a diamine component containing a specific diamine compound with a tetracarboxylic dianhydride, and the polyimine obtained by dehydration ring closure of the polyglycine can be collectively referred to as a polymer.

本發明之聚合體係使用下述式[1]所表示之二胺化合物所得。 The polymerization system of the present invention is obtained by using the diamine compound represented by the following formula [1].

(式中,A表示藉由熱而脫離所得之有機基,NHA基為具備n個(n=1或2),相對於胺基(NH2基)存在於鄰位。又,胺基相互間存在於間位或對位)。 (wherein A represents the organic group obtained by heat removal, and the NHA group has n (n = 1 or 2), and is present in the ortho position relative to the amine group (NH 2 group). Exist in meta or para).

又以NHA基為1個為佳,此時係以下述式1a表示。 Further, it is preferable that one NHA group is used, and in this case, it is represented by the following formula 1a.

式[1]中胺基之位置無特別限定,可為二胺無特別限 定,例如下述式[1-1]~[1-4]等,但就液晶配向性及易合成之觀點,較佳為形成式[1-2]、[1-3]所表示之構造般的位置。 The position of the amine group in the formula [1] is not particularly limited, and the diamine may be not particularly limited. For example, in the following formulas [1-1] to [1-4], it is preferable to form the structures represented by the formulas [1-2] and [1-3] from the viewpoints of liquid crystal alignment and easy synthesis. General location.

(式中A表示藉由熱而脫離所得之有機基)。 (wherein A represents the organic group obtained by heat removal).

式[1]中,胺基被取代之苯環中的有機基可被取代,可藉由試劑之取得性等而作各種選擇,但特佳為未取代之物。 In the formula [1], the organic group in the benzene ring in which the amine group is substituted may be substituted, and various choices may be made by the availability of the reagent, etc., but it is particularly preferably an unsubstituted product.

式[1]中藉由熱而脫離所得之有機基A可為,以熱分解而脫離轉變為胺基之有機基無特別限定。當然具備A之狀態下,係為降低胺基之反應性之物。以熱而脫離所得之A之構造如,苄氧基羰基、9-芴基甲氧基羰基、烯丙氧基羰基、三級丁氧級羰基等所代表之胺基甲酸酯系有機基,但就藉由熱而脫離之效率良好、可以較低之溫度脫離、脫離時所排出之氣體無害之觀點特佳為三級丁氧基羰基。 The organic group A obtained by the heat removal in the formula [1] may be an organic group which is thermally decomposed to be converted into an amine group, and is not particularly limited. Of course, in the state of having A, it is a substance which reduces the reactivity of an amine group. a structure in which A is obtained by heat, such as a urethane-based organic group represented by a benzyloxycarbonyl group, a 9-fluorenylmethoxycarbonyl group, an allyloxycarbonyl group, a tertiary butoxycarbonyl group, or the like, However, it is preferable that the gas which is detached by heat is good, can be detached at a lower temperature, and the gas discharged at the time of detachment is harmless, and is preferably a tertiary oxycarbonyl group.

<二胺化合物> <Diamine compound>

特佳之構造為,下述式所表示之二胺化合物,其為新 穎之化合物。 A particularly preferred structure is a diamine compound represented by the following formula, which is new Ying compound.

下面將說明以新穎的本發明之二胺化合物為例之作用效果,因上述式[1]所表示之本發明所使用的二胺化合物也具有相同之作用效果,故省略重覆說明。 The effect of the novel diamine compound of the present invention will be described below. Since the diamine compound used in the present invention represented by the above formula [1] also has the same effects, the description thereof will be omitted.

本發明之二胺化合物的特徵為,被三級丁氧基羰基(以下稱為Boc基)保護之芳香族胺基接鄰(鄰位)於其他胺基。一般胺基為富有反應性之有機基,因此難直接應用為二胺之支鏈之一部分,但藉由被Boc基保護可降低胺基之反應性,又,以約150℃以上加熱被Boc基保護之胺基時可變化為由Boc基脫保護之胺基。另外因Boc基具有容積較高之三級丁基,故可提升單體之溶解性,且使用該單體所生成之聚合物同樣可提升溶解性。 The diamine compound of the present invention is characterized in that an aromatic amine group protected by a tertiary butoxycarbonyl group (hereinafter referred to as a Boc group) is adjacent (ortho) to other amine groups. Generally, the amine group is a reactive organic group, so it is difficult to directly apply it as a part of the branch of the diamine, but the reactivity of the amine group can be lowered by being protected by the Boc group, and the Boc group is heated by heating at about 150 ° C or higher. The protected amine group can be changed to an amine group deprotected by a Boc group. In addition, since the Boc group has a higher volume of the tertiary butyl group, the solubility of the monomer can be improved, and the polymer formed by using the monomer can also improve the solubility.

胺基為反應性較高之有機基,已知可與不飽和鍵、羧酸、羧酸酐、環氧化合物、羰基等各種部位反應。另外如下述圖所示般將被Boc保護之胺基配置於接近醯胺鍵、酯鍵等之含有羰基之鍵結基時,不易於分子間而易於分子內發生反應,例如本發明之二胺適用於聚醯胺時 可衍生聚苯并咪唑[scheme-1],應用於聚醯胺酸及聚醯亞胺等時,例如具有羧酸部位之聚苯并咪唑衍生物及具有胺基之聚醯亞胺,又,再將該等脫水反應可衍生具有(1H-苯并[d]吡咯并[1,2-a]咪唑-1-酮)般之環構造之聚合物[scheme-2]般。 The amine group is an organic group having high reactivity, and it is known to react with various sites such as an unsaturated bond, a carboxylic acid, a carboxylic acid anhydride, an epoxy compound, and a carbonyl group. Further, when the Boc-protected amine group is disposed near a carbonyl group-containing bonding group such as a guanamine bond or an ester bond as shown in the following figure, it is not easy to cause intramolecular reaction in the molecule, for example, the diamine of the present invention. When applied to polyamine Derivatized polybenzimidazole [scheme-1], when used in poly-proline and polyimine, for example, a polybenzimidazole derivative having a carboxylic acid moiety and a polyimine having an amine group, These dehydration reactions can be carried out in the same manner as the polymer [scheme-2] having a ring structure of (1H-benzo[d]pyrrolo[1,2-a]imidazol-1-one).

本發明之二胺化合物具有,例如與四羧酸二酐反應而形成具有被Boc基保護之胺基的聚醯亞胺先驅物或聚醯亞胺之塗膜後,藉由焙燒使Boc基脫離而生成胺基後;於分子內進行反應形成雜環之特性。又,推測脫離Boc基之胺基非全部消耗於環化反應,而係部分消耗於分子間反應(即交聯反應)。 The diamine compound of the present invention has, for example, a reaction film formed by reacting with a tetracarboxylic dianhydride to form a polyimine precursor or a polyimine having an amine group protected by a Boc group, and then detaching the Boc group by baking After the formation of the amine group, the reaction is carried out in the molecule to form a heterocyclic ring. Further, it is presumed that all of the amine groups desorbed from the Boc group are consumed in the cyclization reaction, and the system is partially consumed in the intermolecular reaction (that is, the crosslinking reaction).

該類藉由脫離Boc基所生成之胺基的反應,推斷可提升膜強度,又藉由與聚合物中之低分子成分交聯推斷可提升信賴性。因此使用本發明二胺之聚醯胺酸或聚醯亞胺於摩擦處理時不易發生膜削減,可得既使長期間高溫下或曝露於背光下也不易降低電壓保持率之效果。 By decomposing the reaction of the amine group formed by the Boc group, it is inferred that the film strength can be increased, and the reliability can be improved by inferring the crosslinking with the low molecular component in the polymer. Therefore, the polyamine or the polyimine which uses the diamine of the present invention is less likely to cause film reduction during the rubbing treatment, and it is possible to obtain an effect of lowering the voltage holding ratio even at a high temperature for a long period of time or under exposure to a backlight.

又可以較低之溫度脫離容積較高之Boc基,及轉化為液晶配向性良好之構造,故可使耐摩擦性與液晶配向性兩立。另外焙燒所生成之構造(雜環)為電氣化學上具有活性之構造,故推斷可賦予低RDC化。特別是組合芳香族之四羧酸二酐與本發明二胺時推斷相互間具有較強之相互作用,因此可得非常難蓄積RDC之配向膜。 Further, it is possible to separate the Boc group having a relatively high volume from a lower temperature and convert it into a structure having a good liquid crystal alignment property, so that the rubbing resistance and the liquid crystal alignment property can be established. Further, since the structure (heterocyclic ring) formed by the calcination is electrochemically active, it is estimated that low RDC can be imparted. In particular, when a combination of an aromatic tetracarboxylic dianhydride and a diamine of the present invention is inferred to have a strong interaction with each other, it is extremely difficult to accumulate an alignment film of RDC.

<二胺化合物之合成方法> <Synthesis method of diamine compound>

下面將說明本發明之二胺的主要合成法。又,下面所說明之方法為合成例,非限定於該例。 The main synthesis of the diamine of the present invention will be explained below. Further, the method described below is a synthesis example, and is not limited to this example.

本發明之二胺可藉由,經各步驟合成二硝基物後,以一般所使用之還原反應將硝基轉變為胺基而得目的之二胺。 The diamine of the present invention can be obtained by converting a nitro group into an amine group by a reduction reaction generally used after synthesizing a dinitro group in each step.

合成二硝基物之具體合成法如實施例所示,例如使硝基與胺基接近般之二硝基胺基苯衍生物或使胺基相互間接近般之單硝基二胺基苯與碳酸三級丁酯等之可熱脫保護的保護試劑反應之方法。 The specific synthesis method for synthesizing the dinitro compound is as shown in the examples, for example, a dinitroaminobenzene derivative having a nitro group similar to an amine group or a mononitrodiaminobenzene having an amine group close to each other. A method for reacting a thermally deprotectable protective reagent such as a tertiary butyl carbonate.

必要時上述反應係於鹼之存在下進行。所使用之鹼可為能合成下無特別限定,例如碳酸鉀、碳酸鈉、碳酸銫、烷氧化鈉、烷氧化鉀、氫氧化鈉、氫氧化鉀、氫化鈉等之無機鹼、吡啶、二甲基胺基吡啶、三甲基胺、三乙基胺、三丁基胺等之有機鹼等。另外藉由所使用之鹼而以二個保護基取代一個胺基時,需慎選適當之鹼。又以氫化鈉等之鹼可有效率取出胺基之氫而為佳,但可以其他之方法合成,無特別限定合成法。 The above reaction is carried out in the presence of a base as necessary. The base to be used may be any inorganic base, pyridine or dimethyl which is not particularly limited, for example, potassium carbonate, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide or sodium hydride. An organic base such as aminopyridine, trimethylamine, triethylamine or tributylamine. In addition, when one amine group is substituted with two protecting groups by the base to be used, a suitable base needs to be carefully selected. Further, it is preferable to take out the hydrogen of the amine group with a base such as sodium hydride, but it can be synthesized by other methods, and the synthesis method is not particularly limited.

還原二硝基化合物之方法無特別限制,一般為以鈀-碳、氧化鉑、阮內鎳、鉑黑、銠-氧化鋁、硫化鉑碳等為觸媒,於乙酸乙酯、甲苯、四氫呋喃、二噁烷、醇系等之溶劑中,藉由氫氣、肼、氯化氫等進行還原之方 法。必要時可使用高壓鍋等。另外構造中含有不飽和鍵部位時,使用鈀碳或鉑碳等還原不飽和鍵時,恐形成飽和鍵,因此較佳之條件為,以還原鐵或錫、氯化錫等之過鍍金屬為觸媒之還原條件。 The method for reducing the dinitro compound is not particularly limited, and generally, palladium-carbon, platinum oxide, Raney nickel, platinum black, ruthenium-alumina, and platinum sulfide carbon are used as a catalyst, and ethyl acetate, toluene, tetrahydrofuran, a solvent which is reduced by hydrogen, helium, hydrogen chloride or the like in a solvent such as dioxane or an alcohol system. law. Use a pressure cooker or the like if necessary. When the structure contains an unsaturated bond, when a unsaturated bond is reduced by using palladium carbon or platinum carbon or the like, a saturated bond is formed. Therefore, it is preferable to use a reduced metal such as reduced iron or tin or tin chloride. The conditions for the restoration of the media.

<式(2)所表示之二胺> <Diamine represented by formula (2)>

本發明之聚合物除了上述式[1]所表示之二胺化合物外,可使用下述式[2]所表示之二胺。 In addition to the diamine compound represented by the above formula [1], the diamine represented by the following formula [2] can be used as the polymer of the present invention.

上述式[2]中R1、X1、X2、X3、p、q、r及R2同上述定義。上述式[2]之二胺為,對增加液晶之預傾角(相對於液晶配向膜的液晶之傾斜角度)具有貢獻之物,該等二胺較佳為具有長鏈烷基、全氟烷基、芳香族環狀基、脂肪族環狀基,及組合該等之取代基、巢類骨架基等之二胺。 In the above formula [2], R 1 , X 1 , X 2 , X 3 , p, q, r and R 2 are as defined above. The diamine of the above formula [2] is a substance which contributes to an increase in the pretilt angle of the liquid crystal (inclination angle with respect to the liquid crystal of the liquid crystal alignment film), and the diamine preferably has a long-chain alkyl group and a perfluoroalkyl group. An aromatic cyclic group, an aliphatic cyclic group, and a diamine in which such a substituent or a nest-based skeleton group is combined.

預傾角之較佳角度會因形態而異,但可藉由上述二胺之構造、導入量之各種選擇而得較佳之預傾角。 The preferred angle of the pretilt angle varies depending on the form, but a preferred pretilt angle can be obtained by various configurations of the diamine structure and the amount of introduction.

式[2]所表示之支鏈二胺中,較佳為要求3至5°之較低預傾角的TN形態,及要求8至20°之預傾角的 OCB形態等之含有較低傾斜發現能的支鏈二胺。 Among the branched diamines represented by the formula [2], a TN form requiring a lower pretilt angle of 3 to 5° and a pretilt angle of 8 to 20° are preferable. A branched diamine having a lower tilt finding ability, such as an OCB form.

傾斜發現能較小之構造中,R1較佳為-O-,或-NHCO-(-CONH-),式中p較佳為0至1,q較佳為0至1,r較佳為0,又,p及/或q為1時,R2較佳為碳數1至12之直鏈烷基,p=q=r=0時,R2較佳為碳數10至22之直鏈烷基或由具有巢類骨架之碳數12至25之有機基中選出之2價有機基。傾斜發現能較小之支鏈二胺的具體構造非限定於表1所示。 In the structure in which the tilt is found to be small, R 1 is preferably -O-, or -NHCO-(-CONH-), wherein p is preferably 0 to 1, q is preferably 0 to 1, and r is preferably 0, further, when p and/or q is 1, R 2 is preferably a linear alkyl group having 1 to 12 carbon atoms, and when p = q = r = 0, R 2 is preferably a carbon number of 10 to 22 An alkyl group or a divalent organic group selected from the group consisting of 12 to 25 carbon atoms having a nest skeleton. The specific structure in which the branching diamine which can be found to be small is not limited to those shown in Table 1.

就電特性觀點較佳為,表1之[2-1]至[2-3]所表示之長鏈烷基支鏈,就液晶配向性,預傾角之安定性之觀點較佳為表1之[2-25]至[2-27]所表示之二胺。特別是[2-25]所表示之二胺併用式[A]所表示之二胺時可得預傾角之面內均勻性優良的液晶配向劑而為佳。 From the viewpoint of electrical properties, it is preferred that the long-chain alkyl branch represented by [2-1] to [2-3] of Table 1 is preferably in the form of liquid crystal alignment and pretilt stability. [2-25] to the diamine represented by [2-27]. In particular, when the diamine represented by the formula [A] is used in combination with the diamine represented by the formula [A], a liquid crystal alignment agent having excellent in-plane uniformity of the pretilt angle is preferable.

另外VA形態等併用傾斜發現能較大之支鏈可得垂直配向性。VA形態中式[2]之較佳構造為,式中R1較佳為-O-、-COO-或-CH2O-,p較佳為0至1,q較佳為0至1,r較佳為0至1,R2較佳為2至22。p=q=r=0時,R2較佳為碳數18至22之直鏈烷基,或具有巢類骨架之碳數12至25之有機基的2價有機基。傾斜發現能較大之支鏈二胺的具體構造如表2-1及表2-2所示。 In addition, the VA form and the like can be found by tilting to obtain a larger alignment to obtain vertical alignment. A preferred configuration of the formula [2] in the VA form is that R 1 is preferably -O-, -COO- or -CH 2 O-, p is preferably 0 to 1, q is preferably 0 to 1, r It is preferably 0 to 1, and R 2 is preferably 2 to 22. When p = q = r = 0, R 2 is preferably a linear alkyl group having 18 to 22 carbon atoms or a divalent organic group having an organic group having 12 to 25 carbon atoms of a nest skeleton. The specific structure of the branched diamine which is found to be large by tilting is shown in Table 2-1 and Table 2-2.

該等二胺具有較高的傾斜發現能,適用於VA形態。特別是[2-43]、[2-92]等二胺因具有較高之傾斜發現能,可以較少之支鏈量得到垂直配向而為佳,又,特別是[2-52]及[2-101]之二胺因具有極高之 傾斜發現能,可以非常少之支鏈量得到垂直配向故有利於配向劑之印刷性觀點。 These diamines have a high tilt discovery energy and are suitable for VA morphology. In particular, diamines such as [2-43] and [2-92] are preferred because they have a higher tilt discovery energy, and a smaller amount of branching can be used for vertical alignment, and in particular, [2-52] and [ 2-101] diamine is extremely high It is found that the tilting can find that the amount of branching can be vertically aligned, which is advantageous for the printing property of the alignment agent.

另外前述式[2]所表示之二胺中,R1較佳為-NHCO-,R2較佳為碳數1至16,更佳為3至10之烷基。又,X1、X2、X3及p、q、r可適當組合。該二胺之構造中,苯環上之各取代基之位置無特別限定,但2個胺基之位置關係較佳為間位或對位。 Further, in the diamine represented by the above formula [2], R 1 is preferably -NHCO-, and R 2 is preferably an alkyl group having 1 to 16 carbon atoms, more preferably 3 to 10 carbon atoms. Further, X 1 , X 2 , X 3 and p, q, and r may be combined as appropriate. In the structure of the diamine, the position of each substituent on the benzene ring is not particularly limited, but the positional relationship between the two amine groups is preferably a meta or para position.

上述式[2]所表示之二胺如,下述式[3]所表示之二胺。 The diamine represented by the above formula [2] is a diamine represented by the following formula [3].

(式[3]中,n為0至21之整數,較佳為0至15之整數)。 (In the formula [3], n is an integer of 0 to 21, preferably an integer of 0 to 15).

上述式[3]所表示之二胺之較佳具體例如下所述,但非限於此。 Preferred specific examples of the diamine represented by the above formula [3] are as follows, but are not limited thereto.

式中n為0至19之整數。n較小時無法發現預傾角,較大時會降低可溶性聚醯亞胺之溶解性。故較佳之n範圍為2至15,更佳為4至10。 Where n is an integer from 0 to 19. When the n is small, the pretilt angle cannot be found, and when it is large, the solubility of the soluble polyimine is lowered. Therefore, the preferred n range is from 2 to 15, more preferably from 4 to 10.

上述[2]所表示之二胺的含量較佳為,全部胺成分中之5至60莫耳%,就預傾之均勻性及印刷性之觀點特佳為5至30莫耳%。 The content of the diamine represented by the above [2] is preferably from 5 to 60 mol% of the total amine component, and particularly preferably from 5 to 30 mol% from the viewpoint of uniformity of pretilt and printability.

又,式[2]所表示之二胺相對於式[1]所表示之二胺1莫耳較佳為含有0.1至1.2莫耳,更佳為0.3至1.0莫耳。式[2]之二胺為該範圍時,可得適當之預傾角及良好之配向性。 Further, the diamine represented by the formula [2] preferably contains 0.1 to 1.2 mol, more preferably 0.3 to 1.0 mol, based on the diamine 1 mole represented by the formula [1]. When the diamine of the formula [2] is in this range, a proper pretilt angle and a good alignment property can be obtained.

上述二胺成分中,可僅為式[1]及[2],但可併用其他二胺。此時之其他二胺無特別限定,例如混合後述之可溶性聚醯亞胺後可使用於製造聚醯胺酸 之二胺。 Among the above diamine components, only the formulas [1] and [2] may be used, but other diamines may be used in combination. The other diamine at this time is not particularly limited, and for example, it can be used for producing polylysine after mixing the soluble polyimine described later. Diamine.

又,與二胺反應後使用於製造可溶性聚醯亞胺之四羧酸二酐成分也如,混合後述之可溶性聚醯亞胺後可使用於製造聚醯胺酸之四羧酸二酐。 Further, the tetracarboxylic dianhydride component which is used in the production of the soluble polyimine after the reaction with the diamine can also be used to produce the polycarboxylic acid tetracarboxylic dianhydride after mixing the soluble polyimine described later.

本發明之液晶配向劑所含的可溶性聚醯亞胺之分子量無特別限定,但就塗膜之強度與作為液晶配向劑用之易處理性的觀點,重量平均分子量較佳為2,000至200,000,更佳為5,000至50,000。 The molecular weight of the soluble polyimine contained in the liquid crystal alignment agent of the present invention is not particularly limited, but the weight average molecular weight is preferably from 2,000 to 200,000, from the viewpoint of the strength of the coating film and the handleability as a liquid crystal alignment agent. Good for 5,000 to 50,000.

[聚醯胺、聚醯胺酸、聚醯胺酸酯、聚醯亞胺] [polyamide, polyglycolic acid, polyamidomate, polyimine]

本發明之聚醯胺為藉由含有式[1]所表示之二胺化合物的二胺成分與二羧酸之鹵化物於鹼之存在下進行反應,或二羧酸與二胺於適當之縮合劑、鹼之存在下進行反應所得的聚醯胺。聚醯胺酸為,藉由含有式[1]所表示之二胺化合物的二胺成分與四羧酸二酐之反應所得的聚醯胺酸。本發明之聚醯胺酸酯為藉由含有式[1]所表示之二胺的二胺成分與四羧酸二酯二氯化物於鹼之存在下進行反應,或四羧酸二酯與二胺於適當之縮合劑、鹼之存在下進行反應所得的聚醯胺酸酯。本發明之聚醯亞胺為藉由該聚醯胺酸脫水閉環,或聚醯胺酸酯加熱閉環所得的聚醯亞胺。該聚醯胺、聚醯胺酸、聚醯胺酸酯及聚醯亞胺均適用為製造液晶配向膜用之聚合物。 The polyamine of the present invention is obtained by reacting a diamine component containing a diamine compound represented by the formula [1] with a halide of a dicarboxylic acid in the presence of a base, or a suitable condensation of a dicarboxylic acid and a diamine. The polyamine which is obtained by carrying out the reaction in the presence of a solvent or a base. Polylysine is a polylysine obtained by reacting a diamine component of a diamine compound represented by the formula [1] with a tetracarboxylic dianhydride. The polyphthalate of the present invention is a reaction of a diamine component containing a diamine represented by the formula [1] with a tetracarboxylic acid diester dichloride in the presence of a base, or a tetracarboxylic acid diester and two A polyphthalate obtained by reacting an amine in the presence of a suitable condensing agent or a base. The polyimine of the present invention is a polyimine obtained by dehydration ring closure of the polyglycolic acid or heating and ring closure of the polyglycolate. The polyamine, polylysine, polyphthalate, and polyimine are all suitable for use in a polymer for producing a liquid crystal alignment film.

製造上述聚醯胺、聚醯胺酸、聚醯胺酸酯、聚醯亞胺用之二胺成分(以下也稱為二胺成分)中,式[1]所表示之二胺之含有比例無限制。 In the above-described diamine component (hereinafter also referred to as a diamine component) for polyamine, polyglycolic acid, polyphthalamide, or polyimine, the content of the diamine represented by the formula [1] is not limit.

二胺成分中,式[1]所表示之二胺未達100莫耳時,所使用的式[1]所表示之二胺以外之二胺無特別限定。其具體例可如下所述。 In the diamine component, when the diamine represented by the formula [1] is less than 100 mol, the diamine other than the diamine represented by the formula [1] to be used is not particularly limited. Specific examples thereof can be as follows.

脂環式二胺類如,1,4-二胺基環己烷、1,3-二胺基環己烷、4,4’-二胺基二環己基甲烷、4,4’-二胺基-3,3’-二甲基二環己基胺、異佛爾酮二胺等。 Alicyclic diamines such as 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamine Base-3,3'-dimethyldicyclohexylamine, isophoronediamine, and the like.

芳香族二胺類如,o-伸苯基二胺、m-伸苯基二胺、p-伸苯基二胺、2,4-二胺基甲苯、2,5-二胺基甲苯、3,5-二胺基甲苯、1,4-二胺基-2-甲氧基苯、2,5-二胺基-p-二甲苯、1,3-二胺基-4-氯苯、3,5-二胺基苯甲酸、1,4-二胺基-2,5-二氯苯、4,4’-二胺基-1,2-二苯基乙烷、4,4’-二胺基-2,2’-二甲基聯苄、4,4’-二胺基二苯基甲烷、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、4,4’-二胺基-3,3’-二甲基二苯基甲烷、2,2’-二胺基芪、4,4’-二胺基芪、4,4’-二胺基二苯基醚、3,4’-二胺基二苯基醚、4,4’-二胺基二苯基硫化物、4,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸、4,4’-二胺基二苯甲酮、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、3,5-雙(4-胺基苯氧基)苯甲酸、4,4’-雙(4-胺基苯氧基)聯苄、2,2-雙[4-胺基苯氧基)甲基]丙烷、2,2- 雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氟基)苯基]碸、1,1-雙(4-胺基苯基)環己烷、α,α-雙(4-胺基苯基)-1,4-二異丙基苯、9,9-雙(4-胺基苯基)芴、2,2-雙(3-胺基苯基)六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、4,4’-二胺基二苯基胺、2,4-二胺基二苯基胺、1,8-二胺基萘、1,5-二胺基萘、1,5-二胺基蒽醌、1,3-二胺基芘、1,6-二胺基芘、1,8-二胺基芘、2,7-二胺基芴、1,3-雙(4-胺基苯基)四甲基二矽氧烷、聯苯胺、2,2’-二甲基聯苯胺、1,2-雙(4-胺基苯基)乙烷、1,3-雙(4-胺基苯基)丙烷、1,4-雙(4-胺基苯基)丁烷、1,5-雙(4-胺基苯基)戊烷、1,6-雙(4-胺基苯基)己烷、1,7-雙(4-胺基苯基)庚烷、1,8-雙(4-胺基苯基)辛烷、1,9-雙(4-胺基苯基)壬烷、1,10-雙(4-胺基苯基)癸烷、1,3-雙(4-胺基苯氧基)丙烷、1,4-(雙(4-胺基苯氧基)丁烷、1,5-雙(4-胺基苯氧基)戊烷、1,6-雙(4-胺基苯氧基)己烷、1,7-雙(4-胺基苯氧基)庚烷、1,8-雙(4-胺基苯氧基)辛烷、1,9-雙(4-胺基苯氧基)壬烷、1,10-雙(4-胺基苯氧基)癸烷、二(4-胺基苯基)丙烷-1,3-醇酯、二(4-胺基苯基)丁烷-1,4-二醇酯、二(4-胺基苯基)戊烷-1,5-二醇酯、二(4-胺基苯基)己烷-1,6-二醇酯、二(4-胺基苯基)庚烷-1,7-二醇酯、二(4-胺基苯基)辛烷-1,8-二醇酯、二(4-胺基苯基)壬烷-1,9-二醇酯、二(4-胺基苯基)癸烷-1,10-二醇 酯、1,3-雙[4-(4-胺基苯氧基)苯氧基]丙烷、1,4-雙[4-(4-胺基苯氧基)苯氧基]丁烷、1,5-雙[4-(4-胺基苯氧基)苯氧基]戊烷、1,6-雙[4-(4-胺基苯氧基)苯氧基]己烷、1,7-雙[4-(4-胺基苯氧基)苯氧基]庚烷、1,8-雙[4-(4-胺基苯氧基)苯氧基]辛烷、1,9-雙[4-(4-胺基苯氧基)苯氧基]壬烷、1,10-雙[4-(4-胺基苯氧基)苯氧基]癸烷等。 Aromatic diamines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3 , 5-diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3 ,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4'-di Amino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminopurine, 4,4'-diaminopurine, 4,4'- Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3, 3'-Diaminodiphenylphosphonium, 4,4'-diaminobenzophenone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-amine Phenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,5-bis(4-aminophenoxy)benzoic acid, 4,4'-bis(4-amino group Phenoxy)bibenzyl, 2,2-bis[4-aminophenoxy)methyl]propane, 2,2- Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-amine) Phenyloxy)phenyl]indole, bis[4-(4-aminophenylfluoro)phenyl]indole, 1,1-bis(4-aminophenyl)cyclohexane, α,α-double (4-Aminophenyl)-1,4-diisopropylbenzene, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis(3-aminophenyl)hexafluoropropane , 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diamino Naphthalene, 1,5-diaminonaphthalene, 1,5-diaminoguanidine, 1,3-diaminoguanidine, 1,6-diaminoguanidine, 1,8-diaminoguanidine, 2, 7-Diaminoguanidine, 1,3-bis(4-aminophenyl)tetramethyldioxane, benzidine, 2,2'-dimethylbenzidine, 1,2-bis(4- Aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,5-bis(4-aminobenzene) Pentane, 1,6-bis(4-aminophenyl)hexane, 1,7-bis(4-aminophenyl)heptane, 1,8-bis(4-aminophenyl) Octane, 1,9-bis(4-aminophenyl)decane, 1,10-bis(4-aminophenyl)decane, 1,3-bis(4-aminophenoxy)propane , 1,4-(bis(4-aminophenoxy)butane, 1, 5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1 , 8-bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane, Bis(4-aminophenyl)propane-1,3-ol ester, bis(4-aminophenyl)butane-1,4-diol ester, bis(4-aminophenyl)pentane- 1,5-diol ester, bis(4-aminophenyl)hexane-1,6-diol ester, bis(4-aminophenyl)heptane-1,7-diol ester, two ( 4-aminophenyl)octane-1,8-diol ester, bis(4-aminophenyl)decane-1,9-diol ester, bis(4-aminophenyl)decane- 1,10-diol Ester, 1,3-bis[4-(4-aminophenoxy)phenoxy]propane, 1,4-bis[4-(4-aminophenoxy)phenoxy]butane, 1 , 5-bis[4-(4-aminophenoxy)phenoxy]pentane, 1,6-bis[4-(4-aminophenoxy)phenoxy]hexane, 1,7 - bis[4-(4-aminophenoxy)phenoxy]heptane, 1,8-bis[4-(4-aminophenoxy)phenoxy]octane, 1,9-double [4-(4-Aminophenoxy)phenoxy]nonane, 1,10-bis[4-(4-aminophenoxy)phenoxy]decane, and the like.

芳香族-脂肪族二胺如,3-胺基苄基胺、4-胺基苄基胺、3-胺基-N-甲基苄基胺、4-胺基-N-甲基苄基胺、3-胺基苯乙基胺、4-胺基苯乙基胺、3-胺基-N-甲基苯乙基胺、4-胺基-N-甲基苯乙基胺、3-(3-胺基丙基)苯胺、4-(3-胺基丙基)苯胺、3-(3-甲基胺基丙基)苯胺、4-(3-甲基胺基丙基)苯胺、3-(4-胺基丁基)苯胺、4-(4-胺基丁基)苯胺、3-(4-甲基胺基丁基)苯胺、4-(4-甲基胺基丁基)苯胺、3-(5-胺基戊基)苯胺、4-(5-胺基戊基)苯胺、3-(5-甲基胺基戊基)苯胺、4-(5-甲基胺基戊基)苯胺、2-(6-胺基萘基)甲基胺、3-(6-胺基萘基)甲基胺、2-(6-胺基萘基)乙基胺、3-(6-胺基萘基)乙基胺等。 Aromatic-aliphatic diamines such as 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine , 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3-( 3-aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylaminopropyl)aniline, 3 -(4-Aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methylaminobutyl)aniline , 3-(5-Aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methylaminopentyl) Aniline, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, 3-(6- Aminonaphthyl)ethylamine and the like.

雜環式二胺類如,2,6-二胺基吡啶、2,4-二胺基吡啶、2,4-二胺基-1,3,5-三嗪、2,7-二胺基二苯并呋喃、3,6-二胺基咔唑、2,4-二胺基-6-異丙基-1,3,5-三嗪、2,5-雙(4-胺基苯基)-1,3,4-噁二唑等。 Heterocyclic diamines such as 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diamino Dibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4-aminophenyl) )-1,3,4-oxadiazole and the like.

脂肪族二胺類如,1,2-二胺基乙烷、1,3- 二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,3-二胺基-2,2-二甲基丙烷、1,6-二胺基-2,5-二甲基己烷、1,7-二胺基-2,5-二甲基庚烷、1,7-二胺基-4,4-二甲基庚烷、1,7-二胺基-3-甲基庚烷、1,9-二胺基-5-甲基庚烷、1,12-二胺基十二烷、1,18-二胺基十八烷、1,2-雙(3-胺基丙氧基)乙烷等。 Aliphatic diamines such as 1,2-diaminoethane, 1,3- Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-di Aminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino- 2,5-Dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7- Diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diaminododecane, 1,18-diaminooctadecane, 1, 2-bis(3-aminopropoxy)ethane or the like.

可併用支鏈具有烷基、含氟之烷基、芳香環、脂肪環、雜環,與由該等所形成之大環狀取代物的二胺化合物。具體例如,下述式[DA-1]至式[DA-30]所表示之二胺化合物。 A diamine compound having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a hetero ring, and a macrocyclic substituent formed by the above may be used in combination. Specifically, for example, a diamine compound represented by the following formula [DA-1] to formula [DA-30].

(式[DA-1]至式[DA-5]中,R6為碳數1至22之烷基或含氟之烷基)。 (In the formula [DA-1] to the formula [DA-5], R 6 is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

(式[DA-6]至式[DA-9]中,S5表示-COO-、-OCO-、-CONH-、-NHCO-、-CH2-、-O-、-CO-或-NH-,R6表示碳數1至22之烷基或含有氟之烷基。 (In the formula [DA-6] to the formula [DA-9], S 5 represents -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 -, -O-, -CO- or -NH -, R 6 represents an alkyl group having 1 to 22 carbon atoms or an alkyl group containing fluorine.

(式[DA-10]至式[DA-11]中,S6表示-O-、-OCH2-、-CH2O-、-COOCH2-或-CH2OCO-,R7為碳數1至22之烷基、烷氧基、含有氟之烷基或含有氟之烷氧基)。 (In the formula [DA-10] to the formula [DA-11], S 6 represents -O-, -OCH 2 -, -CH 2 O-, -COOCH 2 - or -CH 2 OCO-, and R 7 is a carbon number An alkyl group of 1 to 22, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(式[DA-12]至式[DA-14]中,S7表示-COO-、-OCO-、-COHN-、-NHCO-、-COOCH2-、-CH2OCO-、-CH2O-、-OCH2-或-CH2-,R8為碳數1至22之烷基、烷氧基、含氟之烷基或含氟之烷氧基)。 (In the formula [DA-12] to the formula [DA-14], S 7 represents -COO-, -OCO-, -COHN-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O -, -OCH 2 - or -CH 2 -, R 8 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(式[DA-15]及式[DA-16]中,S8表示-COO-、-OCO-、-CONH-、-NHCO-、-COOCH2-、-CH2OCO-、-CH2O-、-OCH2-、-CH2-、-O-或-NH-,R9為氟基、氰基、三氟甲烷基、硝基、偶氮基、甲醯基、乙醯基、乙醯氧基或羥基)。 (In the formula [DA-15] and the formula [DA-16], S 8 represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O -, -OCH 2 -, -CH 2 -, -O- or -NH-, R 9 is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, a Alkoxy or hydroxy).

(式[DA-17]至[DA-20]中,R10為碳數3至12之烷基,1,4-環己烯之順-反異構各自為反體)。 (In the formula [DA-17] to [DA-20], R 10 is an alkyl group having 3 to 12 carbon atoms, and each of the cis-trans isomers of 1,4-cyclohexene is a trans-antibody).

藉由光進行配向處理時,併用一般式[1]之二胺與上述[DA-1]至[DA-30]之二胺可得更安定的預傾角而為佳。可併用之二胺又以[DA-10]至[DA-30]為佳,更佳為[DA-10]至[DA-16]之二胺。該等二胺之較佳含量無特別限定,但較佳為5至50mol%,就印刷性之觀點較佳為5至30mol%。 When the alignment treatment is carried out by light, it is preferred to use a diamine of the general formula [1] and a diamine of the above [DA-1] to [DA-30] to obtain a more stable pretilt angle. The diamine which can be used in combination is preferably [DA-10] to [DA-30], more preferably a diamine of [DA-10] to [DA-16]. The preferred content of the diamine is not particularly limited, but is preferably from 5 to 50 mol%, and is preferably from 5 to 30 mol% from the viewpoint of printability.

又,可併用下述二胺。 Further, the following diamines may be used in combination.

式[DA-35]中,m為0至3之整數,式[DA-38]中,n為1至5之整數。藉由導入[DA-31]及[DA-32]可提升VHR,[DA-33]至[DA-38]具有降低蓄積電荷之效果而為佳。 In the formula [DA-35], m is an integer of 0 to 3, and in the formula [DA-38], n is an integer of 1 to 5. VHR can be improved by introducing [DA-31] and [DA-32], and [DA-33] to [DA-38] have an effect of reducing the accumulated charge.

另外如下述式[DA-39]所表示之二胺基矽氧烷等。 Further, it is a diamine sulfoxane represented by the following formula [DA-39].

(式[DA-39]中,m為1至10之整數)。 (in the formula [DA-39], m is an integer of 1 to 10).

其他之二胺化合物可因應作為液晶配向膜用時之液晶配向性、電壓保持特性、蓄積電荷等之特性,使用1種或混用2種以上。 The other diamine compound may be used alone or in combination of two or more kinds depending on the characteristics of the liquid crystal alignment property, the voltage retention property, and the storage charge when used as a liquid crystal alignment film.

製造本發明之聚醯胺酸用的與二胺成分反應的四羧酸二酐無特別限定。其具體例如下所述。 The tetracarboxylic dianhydride which reacts with the diamine component for producing the polyphthalic acid of the present invention is not particularly limited. This is specifically described below.

具有脂環式構造或脂肪族構造之四羧酸二酐如,1,2,3,4-環丁烷四羧二酐、1,2-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、2,3,4,5-四氫呋喃四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、3,4-二羧基-1-環己基琥珀酸二酐、3,4-二羧基-1,2,3,4-四氫-1-萘琥珀酸二酐、1,2,3,4-丁烷四羧酸二酐、二環[3,3,0]辛烷-2,4,6,8-四羧酸二酐、3,3’,4,4’-二環己基四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、順-3,7-二丁基環辛-1,5-二烯-1,2,5,6-四羧酸二酐、三環[4.2.1.02,5]壬烷-3,4,7,8-四羧酸-3,4:7,8-二酐、六環[6.6.0.12,7.03,6.19,14.010,13]六癸烷-4,5,11,12-四羧酸-4,5:11,12-二酐、4-(2,5-二羧基四氫呋喃-3- 基)-1,2,3,4-四氫萘-1,2-二羧酸酐等。 a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-ring Butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3 , 4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid Dihydride, 1,2,3,4-butanetetracarboxylic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 3,3', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcyclooctane-1,5-diene-1, 2,5,6-tetracarboxylic dianhydride, tricyclo[4.2.1.02,5]decane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride,hexacyclo[ 6.6.0.12, 7.03, 6.19, 14.010, 13] hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dianhydride, 4-(2,5-dicarboxytetrahydrofuran- 3- Base)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and the like.

又,除了上述脂環式構造或脂肪族構造之四羧酸二酐,另使用芳香族四羧酸二酐時,可提升液晶配向性,及減少液晶單元之蓄積電荷而為佳。芳香族四羧酸二酐如,均苯四酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,2’,3,3’-聯苯四羧酸二酐、2,3,3’,4-聯苯四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、2,3,3’,4-二苯甲酮四羧酸二酐、雙(3,4-二羧基苯基)醚二酐、雙(3,4-二羧基苯基)碸二酐、1,2,5,6-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐等。 Further, in addition to the above-mentioned alicyclic structure or aliphatic tetracarboxylic dianhydride, when aromatic tetracarboxylic dianhydride is further used, it is preferable to improve the liquid crystal alignment property and to reduce the accumulated charge of the liquid crystal cell. An aromatic tetracarboxylic dianhydride such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid Anhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4-diphenyl Ketone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 1,2,5,6-naphthalenetetracarboxylic acid Diacetic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like.

製造本發明之聚醯胺酸酯用的與二胺成分反應之四羧酸二烷基酯無特別限制。具體例如下所述。 The dialkyl tetracarboxylic acid to be reacted with the diamine component for producing the polyphthalate of the present invention is not particularly limited. Specifically, for example, as described below.

脂肪族四羧酸二酯之具體例如,1,2,3,4-環丁烷四羧酸二烷基酯、1,2-二甲基-1,2,3,4-環丁烷四羧酸二烷基酯、1,3-二甲基-1,2,3,4-環丁烷四羧酸二烷基酯、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸二烷基酯、1,2,3,4-環戊烷四羧酸二烷基酯、2,3,4,5-四氫呋喃四羧酸二烷基酯、1,2,4,5-環己烷四羧酸二烷基酯、3,4-二羧基-1-環己基琥珀酸二烷基酯、3,4-二羧基-1,2,3,4-四氫-1-萘琥珀酸二烷基酯、1,2,3,4-丁烷四羧酸二烷基酯、二環[3,3,0]辛烷-2,4,6,8-四羧酸二烷基酯、3,3’,4,4’-二環己烷四羧酸二烷基酯、2,3,5-三羧基環戊基乙酸二烷基酯、順-3,7-二丁基環辛- 1,5-二烯-1,2,5,6-四羧酸二烷基酯、三環[4.2.1.02,5]壬烷-3,4,7,8-四羧酸-3,4:7,8-二烷基酯、六環[6.6.0.12,7.03,6.19,14.010,13]十六烷-4,5,11,12-四羧酸-4,5:11,12-二烷基酯、4-(2,5二羰基四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二黃蒿萜酮二烷基酯等。 Specific examples of the aliphatic tetracarboxylic acid diester are, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane IV Dialkyl carboxylate, dialkyl 1, 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylate, 1,2,3,4-tetramethyl-1,2, Dialkyl 3,4-cyclobutanetetracarboxylate, dialkyl 1,2,3,4-cyclopentanetetracarboxylate, dialkyl 2,3,4,5-tetrahydrofuran tetracarboxylate 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3 , dialkyl 4-tetrahydro-1-naphthalene succinate, dialkyl 1,2,3,4-butanetetracarboxylate, bicyclo[3,3,0]octane-2,4, Dialkyl 6,8-tetracarboxylate, dialkyl 3,3',4,4'-dicyclohexanetetracarboxylate, dialkyl 2,3,5-tricarboxycyclopentyl acetate , cis-3,7-dibutylcyclooctane- 1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.02,5]nonane-3,4,7,8-tetracarboxylic acid-3,4 : 7,8-dialkyl ester, hexacyclo[6.6.0.12,7.03,6.19,14.010,13]hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-two Alkyl ester, 4-(2,5-dicarbonyltetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-diythionidone dialkyl ester, and the like.

芳香族四羧酸二烷基酯如,均苯四酸二烷基酯、3,3’,4,4’-聯苯四羧酸二烷基酯、2,2’,3,3’-聯苯四羧酸二烷基酯、2,3,3’,4-聯苯四羧酸二烷基酯、3,3’,4,4’-二苯甲酮四羧酸二烷基酯、2,3,3’,4-二苯甲酮四羧酸二烷基酯、雙(3,4-二羧基苯基)醚二烷基酯、雙(3,4-二羧基苯基)碸二烷基酯、1,2,5,6-萘四羧酸二烷基酯、2,3,6,7-萘四羧酸二烷基酯等。 Dialkyl aromatic tetracarboxylic acid such as dialkyl pyromellitic acid, dialkyl 3,3',4,4'-biphenyltetracarboxylate, 2,2',3,3'- Dialkyl biphenyl tetracarboxylate, dialkyl 2,3,3',4-biphenyltetracarboxylate, dialkyl 3,3',4,4'-benzophenone tetracarboxylate , 2,3,3',4-dibenzophenone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4-dicarboxyphenyl) Dialkyl dialkyl ester, dialkyl 1,2,5,6-naphthalenetetracarboxylate, dialkyl 2,3,6,7-naphthalenetetracarboxylate, and the like.

製造本發明之聚醯胺用的與二胺成分反應之二羧酸無特別限定。二羧酸或其衍生物之脂肪族二羧酸的具體例如,丙二酸、草酸、二甲基丙二酸、琥珀酸、富馬酸、戊二酸、己二酸、黏康酸、2-甲基己二酸、三甲基己二酸、庚二酸、2,2-二甲基戊二酸、3,3-二乙基琥珀酸、壬二酸、癸二酸及辛二酸等之二羧酸。 The dicarboxylic acid to be reacted with the diamine component for producing the polyamine of the present invention is not particularly limited. Specific examples of the aliphatic dicarboxylic acid of the dicarboxylic acid or a derivative thereof include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muric acid, 2 -methyl adipate, trimethyl adipate, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethyl succinic acid, azelaic acid, sebacic acid and suberic acid The dicarboxylic acid.

脂環式系之二羧酸如,1,1-環丙烷二羧酸、1,2-環丙烷二羧酸、1,1-環丁烷二羧酸、1,2-環丁烷二羧酸、1,3-環丁烷二羧酸、3,4-二苯基-1,2-環丁烷二羧酸、2,4-二苯基-1,3-環丁烷二羧酸、1-環丁烯-1,2-二羧酸、1-環丁烯-3,4-二羧酸、1,1-環戊烷二羧 酸、1,2-環己烷二羧酸、1,3-環戊烷二羧酸、1,1-環己烷二羧酸、1,2-環己烷二羧酸、1,3-環己烷二羧酸、1,4-環己基二羧酸、1,4-(2-降冰片烯)二羧酸、降冰片烯-2,3-二羧酸、二環[2.2.2]辛烷-1,4-二羧酸、二環[2.2.2]辛烷-2,3-二羧酸、2,5-二羰基-1,4-二環[2.2.2]辛烷二羧酸、1,3-金剛烷二羧酸、4,8-二羰基-1,3-金剛烷二羧酸、2,6-螺[3.3]庚烷二羧酸、1,3-金剛烷二乙酸、莰烷酸等。 An alicyclic dicarboxylic acid such as 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylate Acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid , 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylate Acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3- Cyclohexanedicarboxylic acid, 1,4-cyclohexyl dicarboxylic acid, 1,4-(2-norbornene) dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2 Octane-1,4-dicarboxylic acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-dicarbonyl-1,4-bicyclo[2.2.2]octane Dicarboxylic acid, 1,3-adamantane dicarboxylic acid, 4,8-dicarbonyl-1,3-adamantane dicarboxylic acid, 2,6-spiro[3.3]heptane dicarboxylic acid, 1,3-gold Alkane diacetic acid, decanoic acid, and the like.

芳香族二羧酸如,o-酞酸、間苯二酸、對苯二酸、5-甲基間苯二酸、5-tert-丁基間苯二酸、5-胺基間苯二酸、5-羥基間苯二酸、2,5-二甲基對苯二酸、四甲基對苯二酸、1,4-萘二羧酸、2,5-萘二羧酸、2,6-萘二羧酸、2,7-萘二羧酸、1,4-蒽二羧酸、1,4-蒽醌二羧酸、2,5-聯苯二羧酸、4,4’-聯苯二羧酸、1,5-伸聯苯基二羧酸、4,4”-三聯苯基二羧酸、4,4’-二苯基甲烷二羧酸、4,4’-二苯基乙烷二羧酸、4,4’-二苯基丙烷二羧酸、4,4’-二苯基六氟丙烷二羧酸、4,4’-二苯基醚二羧酸、4,4’-聯苄基二羧酸、4,4’-芪二羧酸、4,4’-二苯乙炔二羧酸、4,4’-羰基二苯甲酸、4,4’-磺醯二苯甲酸、4,4’-二硫二苯甲酸、p-伸苯基二乙酸、3,3’-p-伸苯基二丙酸、4-羧基肉桂酸、p-伸苯基二丙烯酸、3,3’-[4,4’-(伸甲基二-p-伸苯基)]二丙酸、4,4’-[4,4’-(氧基二-p-伸苯基)]二丙酸、4,4’-[4,4’-(氧基二-p-伸苯基)]二丁酸、(二異亞丙基 二-p-伸苯基二氧基)二丁酸、雙(p-羧基苯基)二甲基矽烷等之二羧酸。 Aromatic dicarboxylic acids such as o-decanoic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid , 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6 -naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-quinone dicarboxylic acid, 1,4-nonanedicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-linked Benzene dicarboxylic acid, 1,5-extended biphenyl dicarboxylic acid, 4,4"-terphenylene dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl Ethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4 '-Dibenzyldicarboxylic acid, 4,4'-nonanedicarboxylic acid, 4,4'-diphenylacetylene dicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4,4'-sulfonyldiphenyl Formic acid, 4,4'-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3'-p-phenylene dipropionic acid, 4-carboxycinnamic acid, p-phenylene diacrylate, 3 , 3'-[4,4'-(Extended methyldi-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene) Dipropionic acid, 4,4'-[4,4'-(oxygen Two -p- phenylene)] bis butanoic acid, (ii isopropylidene Dicarboxylic acid such as di-p-phenylenedioxy)dibutyric acid or bis(p-carboxyphenyl)dimethyloxane.

含有雜環之二羧酸如,1,5-(9-羰基芴)二羧酸、3,4-呋喃二羧酸、4,5-噻唑二羧酸、2-苯基-4,5-噻唑二羧酸、1,2,5-噻二唑-3,4-二羧酸、1,2,5-噁二唑-3,4-二羧酸、2,3-吡啶二羧酸、2,4-吡啶二羧酸、2,5-吡啶二羧酸、2,6-吡啶二羧酸、3,4-吡啶二羧酸、3,5-吡啶二羧酸等。 a dicarboxylic acid containing a heterocyclic ring such as 1,5-(9-carbonylindole)dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5- Thiazol dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, and the like.

上述各種二羧酸可為酸二鹵化物或酐之構造物。該等之二羧酸類中,特別是可賦予直線性構造之聚醯胺的二羧酸類能保有液晶分子之配向性而為佳。該等又以使用對苯二酸、異對苯二酸、1,4-環己烷二羧酸、4,4’-聯苯二羧酸、4,4’-二苯基甲烷二羧酸、4,4’-二苯基乙烷二羧酸、4,4’-二苯基丙烷二羧酸、4,4’-二苯基六氟丙烷二羧酸、2,2-雙(苯基)丙烷二羧酸、4,4-三聯苯基二羧酸、2,6-萘二羧酸、2,5-吡啶二羧酸或該等之酸二鹵化物等為佳。該等化合物中也有存在異構體之物,又可使用含有該等之混合物。又,可併用2種以上之化合物。本發明所使用之二羧酸類非限定於上述化合物例。 The above various dicarboxylic acids may be structures of acid dihalides or anhydrides. Among these dicarboxylic acids, in particular, a dicarboxylic acid which can impart a linear structure to a polyamine can retain the alignment property of liquid crystal molecules. The use of terephthalic acid, isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid , 4,4'-diphenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 2,2-bis(benzene Preference is given to propane dicarboxylic acid, 4,4-triphenyldicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,5-pyridinedicarboxylic acid or such acid dihalides. The isomers are also present in the compounds, and mixtures containing such may also be used. Further, two or more kinds of compounds may be used in combination. The dicarboxylic acid used in the present invention is not limited to the above compound examples.

四羧酸二酐可因應作為液晶配向膜用時之液晶配向性、電壓保持特性、蓄積電荷等之特性,使用1種或併用2種以上。 The tetracarboxylic dianhydride may be used alone or in combination of two or more kinds depending on the characteristics of the liquid crystal alignment property, the voltage retention property, and the storage charge when used as a liquid crystal alignment film.

藉由四羧酸二酐與二胺成分之反應,製 造本發明之聚醯胺酸時,可使用已知之合成方法。一般為,於有機溶劑中使四羧酸二酐與二胺成分反應之方法。四羧酸二酐與二胺之反應於有機溶劑中較易進行,且不發生副產物而為佳。 By reacting tetracarboxylic dianhydride with a diamine component For the production of the poly-proline of the present invention, a known synthesis method can be used. Generally, a method of reacting a tetracarboxylic dianhydride with a diamine component in an organic solvent. The reaction of the tetracarboxylic dianhydride with the diamine is relatively easy to carry out in an organic solvent, and it is preferred that no by-products are generated.

四羧酸二酐與二胺之反應用的有機溶劑可為,能溶解所生成之聚醯胺酸之物無特別限定。其具體例如下所述。 The organic solvent used for the reaction of the tetracarboxylic dianhydride and the diamine may be one which is capable of dissolving the produced polyamic acid, and is not particularly limited. This is specifically described below.

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-乙基-2-吡咯烷酮、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、異丙基醇、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、甲基溶纖劑、乙基溶纖劑、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、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、戊基乙酸酯、 丁基丁酸酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二己基醚、二噁烷、n-己烷、n-戊烷、n-辛烷、二乙基醚、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n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、二聚醚、4-羥基-4-甲基-2-戊酮、3-甲氧基-N,N-二甲基丙醯胺、3-乙氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺等。該等可單獨使用,或混合使用。另外既使為無法溶解聚醯胺酸之溶劑,於不析出所生成之聚醯胺酸之範圍內可混合上述溶劑使用。 N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, two Methyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl Ketone, methyl mercapto ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, B Cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol , propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl 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, three Propylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, Butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, two Ethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy Propionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N - dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropionamide, and the like. These may be used alone or in combination. Further, even if it is a solvent in which polylysine cannot be dissolved, the above solvent can be used in a range in which the polyamic acid formed is not precipitated.

又,有機溶劑中之水分會阻礙聚合反應,而成為所生成之聚醯胺酸水解之原因,因此較佳為盡可能將有機溶劑脫水乾燥再使用。 Further, since the water in the organic solvent hinders the polymerization reaction and causes hydrolysis of the produced polylysine, it is preferred to dehydrate and dry the organic solvent as much as possible.

於有機溶劑中使四羧酸二酐與二胺成分反應之方法如,攪拌二胺成分分散或溶解於有機溶劑所得之溶液下,將四羧酸二酐直接,或分散或溶解於有機溶劑後加入之方法,及相反地將二胺成分加入四羧酸二酐分散或溶解於有機溶劑所得之溶液中之方法,及交互添加四羧酸二酐與二胺成分之方法等,可使用該等任何方法。又,四羧酸二酐或二胺成分係由複數種化合物所形成時,可以預先混合之狀態反應, 或各別依序反應,又可為各別反應而得之低分子量物再混合反應所得之高分子量物。 The method for reacting a tetracarboxylic dianhydride with a diamine component in an organic solvent, for example, stirring a solution in which a diamine component is dispersed or dissolved in an organic solvent, and directly or dispersing or dissolving the tetracarboxylic dianhydride in an organic solvent The method of adding, and conversely, the method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride in an organic solvent, and a method of mutually adding a tetracarboxylic dianhydride and a diamine component, etc., can be used. Any method. Further, when the tetracarboxylic dianhydride or the diamine component is formed of a plurality of compounds, it can be reacted in a state of being mixed in advance. Or the respective high-molecular weight products obtained by the reaction of the low molecular weight substances obtained by the respective reactions.

此時之聚合溫度可由-20℃至150℃之任意溫度中選擇,但較佳為-5℃至100℃之範圍。又,反應可以任意濃度進行,但濃度太低時難得到高分子量聚合物,濃度太高時會過度提升反應液之黏性而難均勻攪拌,因此四羧酸二酐與二胺成分之反應溶液中的合計濃度較佳為1至50質量%,更佳為5至30質量%。反應初期可以高濃度進行,其後追加有機溶劑。 The polymerization temperature at this time may be selected from any of -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C. Further, the reaction can be carried out at any concentration, but when the concentration is too low, it is difficult to obtain a high molecular weight polymer. When the concentration is too high, the viscosity of the reaction liquid is excessively increased and it is difficult to uniformly stir, so that the reaction solution of the tetracarboxylic dianhydride and the diamine component is obtained. The total concentration in the mixture is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then an organic solvent is added.

聚醯胺酸之聚合反應中,四羧酸二酐之合計莫耳數,與二胺成分之合計莫耳數的比值較佳為0.8至1.2。與一般聚縮合反應相同,該莫耳比接近1.0時可增加所生成之聚醯胺酸的分子量。 In the polymerization reaction of polyamic acid, the ratio of the total number of moles of tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably from 0.8 to 1.2. As with the general polycondensation reaction, when the molar ratio is close to 1.0, the molecular weight of the produced poly-proline is increased.

本發明之聚醯亞胺為,前述聚醯胺酸脫水閉環所得之聚醯亞胺,適用為製造液晶配向膜用之聚合物。 The polyimine of the present invention is a polyimine obtained by dehydration ring closure of the polyamic acid, and is preferably used as a polymer for producing a liquid crystal alignment film.

本發明之聚醯亞胺中,聚胺酸基之脫水閉環率(醯亞胺化率)非必需為100%,可因應用途及目的任意調整。 In the polyimine of the present invention, the dehydration ring closure ratio (the imidization ratio) of the polyamino acid group is not necessarily 100%, and can be arbitrarily adjusted depending on the purpose and purpose.

[聚醯亞胺] [polyimine]

將聚醯胺酸醯亞胺化之方法如,直接將聚醯胺酸之溶液加熱的熱醯亞胺化、將觸媒加入聚醯胺酸之溶 液的觸媒醯亞胺化。 The method for imidating polyphosphonium hydrazide, for example, directly heat-heating a solution of a poly-proline acid solution, and adding a catalyst to the solution of poly-proline The catalyst of the liquid is imidized.

於溶液中將聚醯胺酸熱醯亞胺化時之溫度為100℃至400℃,較佳為120℃至250℃,又以將藉由醯亞胺化反應所生成之水排出系外的同時進行之方法為佳。 The temperature at which the polyglycolic acid is imidized in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water formed by the hydrazine imidization reaction is discharged outside the system. The method carried out at the same time is better.

聚醯胺酸之觸媒醯亞胺化可藉由,將鹼性觸媒與酸酐加入聚醯胺酸之溶液中,於-20至250℃,較佳於0至180℃下攪拌之方法進行。鹼性觸媒之含量為醯胺酸基之0.5至30莫耳倍,較佳為2至20莫耳倍,酸酐之含量為醯胺酸基之1至50莫耳倍,較佳為3至30莫耳倍。鹼性觸媒如,吡啶、三乙基胺、三甲基胺、三丁基胺、三辛基胺等,其中又以吡啶於進行反應時具有適當鹼性而為佳。酸酐如,乙酸酐、偏苯三酸酐、均苯四酸酐等,其中又以使用乙酸酐時結束反應後易精製而為佳。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,反應時間而控制。 The ruthenium imidization of polylysine can be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid, and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. . The content of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the guanyl group, and the content of the acid anhydride is 1 to 50 moles, preferably 3 to the amidate group. 30 moles. The basic catalyst is, for example, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine or the like, and it is preferred that pyridine is appropriately alkaline when it is reacted. The acid anhydride is, for example, acetic anhydride, trimellitic anhydride, pyromellitic anhydride or the like, and it is preferred to use an acetic anhydride to complete the reaction and then to refine it. 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.

[聚醯胺酸酯] [polyamidomate]

合成聚醯胺酸酯之方法可為,藉由四羧酸二酯二氯化物與二胺之反應,或適當之縮合劑、鹼之存在下使四羧酸二酯與二胺反應,可得聚醯亞胺之先驅物之一種的聚醯胺酸酯。又可由,預先聚合聚醯胺酸,利用高分子反應使醯胺酸中之羧酸酯化所得。 The method for synthesizing the polyphthalate ester can be obtained by reacting a tetracarboxylic acid diester dichloride with a diamine or a suitable condensing agent or a base to react a tetracarboxylic acid diester with a diamine. A polyglycolate of one of the precursors of polyimine. Further, it is also possible to prepolymerize polylysine and esterify the carboxylic acid in valeric acid by a polymer reaction.

具體上可藉由,鹼與有機溶劑之存在下於-20℃至150℃,較佳於0℃至50℃下使四羧酸二酯二氯化物與二胺反應30分鐘至24小時,較佳為1至4小時而合成。 Specifically, the tetracarboxylic acid diester dichloride can be reacted with the diamine in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably at 0 ° C to 50 ° C for 30 minutes to 24 hours. It is synthesized for 1 to 4 hours.

前述鹼可使用吡啶、三乙基胺、4-二甲基胺基吡啶,但就穩定進行反應較佳為吡啶。鹼之添加量就易去除之量且易得高分子量物之觀點,相對於四羧酸二酯二氯化物較佳為2至4倍莫耳。 As the base, pyridine, triethylamine or 4-dimethylaminopyridine can be used, but the reaction is preferably carried out stably. The amount of the base to be added is preferably from 2 to 4 times the molar amount relative to the tetracarboxylic acid diester dichloride from the viewpoint of easy removal amount and easy availability of a high molecular weight substance.

縮合劑之存在下進行縮合聚合時可使用三苯基亞磷酸酯、二環己基碳化二亞胺、1-乙基-3-(3-二甲基胺基丙基)碳化二亞胺鹽酸鹽、N,N-羰基二咪唑、二甲氧基-1,3,5-三嗪基甲基嗎啉鎓、O-(苯并三唑-1-基)-N,N,N’,N’-四甲基脲鎓四氟硼酸鹽、O-(苯并三唑-1-基)-N,N,N’,N’-四甲基脲鎓六氟亞磷酸鹽、(2,3-二氫-2-硫基-3-苯并噁唑基)膦酸二苯酯、4-(4,6-二甲氧基-1,3,5-三嗪-2-基)4-甲氧基嗎啉鎓氯化物n-水合物等。 Triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride may be used in the condensation polymerization in the presence of a condensing agent. Salt, N,N-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N', N'-tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphite, (2, 3-dihydro-2-thio-3-benzooxazolylphosphonic acid diphenyl ester, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)4 - methoxymorpholinium chloride chloride n-hydrate, and the like.

又,使用上述縮合劑之方法中,添加路易斯酸之添加劑可有效率進行反應。路易斯酸較佳為,氯化鋰、溴化鋰等之鹵化鋰。路易斯酸之添加量相對於(C1)較佳為0.1至1.0倍莫耳量。 Further, in the method using the above condensing agent, the addition of the Lewis acid additive can efficiently carry out the reaction. The Lewis acid is preferably a lithium halide such as lithium chloride or lithium bromide. The addition amount of the Lewis acid is preferably 0.1 to 1.0 times the molar amount with respect to (C1).

上述反應所使用之溶劑可為,上述聚合聚醯胺酸時所使用之溶劑,但就單體及聚合物之溶解性較佳為N-甲基-2-吡咯熔酮、γ-丁內酯,該等可使 用1種或混合2種以上。合成時之濃度就不易發生聚合物析出,且易得高分子量物之觀點較佳為1至30質量%,更佳為5至20質量%。又,為了防止四羧酸二酯二氯化物水解,較佳為盡可能將聚醯胺酸酯合成用之溶劑脫水,置於氮環境中防止外氣混入。 The solvent used in the above reaction may be the solvent used in the above polymerization of polyamic acid, but the solubility of the monomer and the polymer is preferably N-methyl-2-pyrrolidinone or γ-butyrolactone. , these can make One type or a mixture of two or more types. The concentration at the time of synthesis is less likely to cause precipitation of the polymer, and the viewpoint of easily obtaining a high molecular weight substance is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferred to dehydrate the solvent for the synthesis of the polyphthalate as much as possible, and to prevent the incorporation of outside air in a nitrogen atmosphere.

[聚醯胺] [polyamide]

聚醯胺也可由聚醯胺酸酯相同之方法合成。 Polyamine can also be synthesized by the same method as polyglycolate.

[聚合物回收] [polymer recovery]

由聚醯胺酸、聚醯胺酸酯、聚醯亞胺之反應溶液,回收所生成之聚醯胺酸、聚醯胺酸酯、聚醯亞胺時,可將反應溶液投入弱溶劑內使其沈澱。沈澱用之弱溶劑如,甲醇、丙酮、己烷、丁基溶纖劑、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯、苯、水等。投入弱溶劑後將沈澱的聚合物過濾回收後,可於常壓或減壓下以常溫或加熱進行乾燥。又,將沈澱回收之聚合物再溶解於有機溶劑內,重覆該再沈澱回收之操作2至10次後,可減少聚合物之不純物。此時之弱溶劑如,醇類、酮類、烴等,使用由其中選出之3種以上之弱溶劑時,可進一步提升精製效率而為佳。 When recovering the produced polyglycolic acid, polyphthalate, or polyimine from a reaction solution of polyglycolic acid, polyphthalate, or polyimine, the reaction solution can be put into a weak solvent. It precipitates. Weak solvents for precipitation are, for example, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. After the weak solvent is introduced, the precipitated polymer is collected by filtration, and then dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the precipitate-recovered polymer is redissolved in an organic solvent, and after repeating the reprecipitation recovery operation for 2 to 10 times, the impurity of the polymer can be reduced. When a weak solvent at this time is used, for example, an alcohol, a ketone, a hydrocarbon, or the like, when three or more kinds of weak solvents selected from the above are used, the purification efficiency can be further improved.

本發明之液晶配向劑所含的聚醯胺酸及聚醯亞胺之分子量,考量由其所得之塗膜的強度,及 塗膜形成時之作業性、塗膜之均勻性時,以GPC(Gel Permeation Chromatography)法測定之重量平均分子量較佳為5,000至1,000,000,更佳為10,000至150,000。 The molecular weight of the poly-proline and the polyimine contained in the liquid crystal alignment agent of the present invention, considering the strength of the coating film obtained therefrom, and When the workability at the time of coating film formation and the uniformity of the coating film are used, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<液晶配向劑> <Liquid alignment agent>

本發明之液晶配向劑為,形成液晶配向膜用之塗佈液,形成樹脂塗膜用之樹脂成分溶解於有機溶劑所得之溶液。此時之前述樹脂成分為,含有由上述本發明之聚合物中選出之至少一種之聚合物的樹脂成分。此時樹脂成分之含量較佳為1質量%至20質量%,更佳為3質量%至15質量%,特佳為3質量%至10質量%。 The liquid crystal alignment agent of the present invention is a solution obtained by forming a coating liquid for a liquid crystal alignment film and forming a resin component for a resin coating film dissolved in an organic solvent. The resin component at this time is a resin component containing a polymer selected from at least one of the polymers of the present invention. The content of the resin component at this time is preferably from 1% by mass to 20% by mass, more preferably from 3% by mass to 15% by mass, particularly preferably from 3% by mass to 10% by mass.

本發明中,前述樹脂成分可會為本發明所使用之共聚物,又可混合本發明之聚合物與其他之聚合物。此時樹脂成分中本發明之聚合物以外之其他聚合物的含量為0.5質量%至15質量%,較佳為1質量%至10質量%。 In the present invention, the above-mentioned resin component may be a copolymer used in the present invention, and a polymer of the present invention and other polymers may be mixed. The content of the polymer other than the polymer of the present invention in the resin component at this time is from 0.5% by mass to 15% by mass, preferably from 1% by mass to 10% by mass.

該其他聚合物如,與四羧酸二酐成分反應之二胺成分係使用特定二胺化合物以外之二胺化合物所得的聚醯胺酸或聚醯亞胺等。 The other polymer, for example, a diamine component which is reacted with a tetracarboxylic dianhydride component, is a polyamic acid or a polyimine obtained by using a diamine compound other than a specific diamine compound.

本發明之液晶配向劑所使用的有機溶劑可為,能溶解樹脂成分之有機溶劑無特別限定。其具體例如下所述。 The organic solvent used in the liquid crystal alignment agent of the present invention may be any organic solvent capable of dissolving the resin component, and is not particularly limited. This is specifically described below.

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-甲基己內醯胺、2-吡咯烷酮、N-乙基吡咯烷酮、N-乙烯基吡咯烷酮、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、3-甲氧基-N,N-二甲基丙醯胺、3-乙氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、1,3-二甲基-咪唑啉酮、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、環己酮、碳酸乙烯酯、碳酸丙烯酯、二聚醚、4-羥基-4-甲基-2-戊酮等。該等可單獨使用,或混合使用。 N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, 3-methoxy-N,N-dimethylpropyl Indoleamine, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, B Kefenyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diether, 4-hydroxyl -4-methyl-2-pentanone and the like. These may be used alone or in combination.

本發明之液晶配向劑可含有上述以外之成分。其例如,提升塗佈液晶配向劑時之膜厚均勻性及表面平滑性的溶劑及化合物、提升液晶配向膜與基板之密合性的化合物等。 The liquid crystal alignment agent of the present invention may contain components other than the above. For example, a solvent and a compound which improve film thickness uniformity and surface smoothness when a liquid crystal alignment agent is applied, a compound which improves adhesion between a liquid crystal alignment film and a substrate, and the like are used.

提升膜厚之均勻性及表面平滑性的溶劑(弱溶劑)之具體例如下所述。 Specific examples of the solvent (weak solvent) for improving the uniformity of the film thickness and the surface smoothness are as follows.

例如,異丙基醇、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、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基 醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、戊基乙酸酯、丁基丁酸酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二己基醚、1-己醇、n-己烷、n-庚烷、n-辛烷、二乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、1-甲氧基-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-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲基酯、乳酸乙基酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊基酯等之具有低表面張力之溶劑等。 For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Kikabi alcohol, 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-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl 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 isobutyl ether, diisobutylene, pentyl acetic acid Ester, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-heptane, n-octyl Alkane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propyl propionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropane Acid propyl ester, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-benzene Oxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl -2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, lactic acid A solvent having a low surface tension such as isoamyl ester or the like.

該等弱溶劑可使用1種或混合複數種。使用上述般之溶劑時,較佳為液晶配向劑所含的溶劑全體之5至80質量%,更佳為20至60質量%。 These weak solvents may be used alone or in combination of plural kinds. When the solvent is used as described above, it is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass based on the total of the solvent contained in the liquid crystal alignment agent.

提升膜厚之均勻性及表面平滑性的化合物如,氟系表面活性劑、聚矽氧系表面活性劑、非離 子系表面活性劑等。 Compounds which increase the uniformity of film thickness and surface smoothness, such as fluorine-based surfactants, polyoxynitride surfactants, non-detached Sub-system surfactants, etc.

更具體如,耶佛特EF301、EF303、EF352(特肯姆公司製)、美蓋范F171、F173、R-30(大日本印刷公司製)、佛洛拉FC430、FC431(住友3M公司製)、艾薩西AG710、薩佛隆S-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子公司製)等。該等表面活性劑之使用比例,相對於液晶配向劑所含之樹脂成分100質量份,較佳為0.01至2質量份,更佳為0.01至1質量份。 More specifically, Yvette EF301, EF303, EF352 (manufactured by Tecom Co., Ltd.), Meiga FAN, F173, F173, R-30 (manufactured by Dainippon Printing Co., Ltd.), Flora FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.) , Isaishi AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment agent.

提升液晶配向膜與基板之密合性的化合物具體例如,下述含有官能性矽烷之化合物及含有環氧基之化合物等。 Specific examples of the compound for improving the adhesion between the liquid crystal alignment film and the substrate include, for example, a compound containing a functional decane, a compound containing an epoxy group, and the like.

例如,3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽烷基丙基三伸乙基三胺、N-三甲氧基矽烷基丙基三伸乙基三胺、10-三甲氧基矽烷基-1,4,7-三氮雜癸烷、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯、N-苄基-3-胺基丙基三 甲氧基矽烷、N-苄基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧基伸乙基)-3-胺基丙基三甲氧基矽烷、N-雙(氧基伸乙基)-3-胺基丙基三乙氧基矽烷、乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、甘油二縮水甘油醚、2,2-二溴新戊二醇二縮水甘油醚、1,3,5,6-四縮水甘油基-2,4-己二醇、N,N,N’,N’-四縮水甘油醚-m-二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N’,N’-四縮水甘油基-4,4’-二胺基二苯基甲烷等。 For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxy decane, 3-ureidopropyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyltrimethoxy decane, N-ethoxycarbonyl-3-aminopropyl three Ethoxy decane, N-triethoxydecyl propyl triethylidene triamine, N-trimethoxydecyl propyl triethylidene triamine, 10-trimethoxydecyl-1,4, 7-Triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecane-3,6-diazaindolyl acetate, 9 -triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyl three Methoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltri Ethoxy decane, N-bis(oxyethyl)-3-aminopropyltrimethoxydecane, N-bis(oxyethyl)-3-aminopropyltriethoxydecane, ethylene Alcohol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane Alcohol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N,N',N'-tetraglycidyl ether-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane or the like.

除了提升基板與膜之密合性外,為了防止因背光而降低電特性等可另導入酚醛塑料系之添加劑。具體之酚醛塑料系添加劑如下所述,但其構造無限定。 In addition to improving the adhesion between the substrate and the film, in order to prevent the electrical characteristics from being lowered by the backlight, an additive of the phenolic plastic type may be additionally introduced. The specific phenolic plastic additive is as follows, but its structure is not limited.

使用提升與基板之密合性的化合物時,其使用量相對於液晶配向劑所含之樹脂成分100質量份較佳為0.1至30質量份,更佳為1至20質量份。使用量未達0.1質量份時將無法期待密合性提升效果,多於30質量份時會使液晶之配向性變差。 In the case of using a compound which improves the adhesion to the substrate, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment agent. When the amount used is less than 0.1 part by mass, the adhesion improving effect cannot be expected, and when it is more than 30 parts by mass, the alignment of the liquid crystal is deteriorated.

本發明之液晶配向劑中,除了上述於無損本發明之效果之範圍內,為了改變液晶配向膜之電容率及導電性等之電特性,可添加介電體及導電物質,又,為了提高作為液晶配向膜用時之膜硬度及細密度可添加交聯性化合物。 In the liquid crystal alignment agent of the present invention, in order to change the electrical properties such as the permittivity and conductivity of the liquid crystal alignment film, a dielectric material and a conductive material may be added in addition to the above-described effects of the present invention. A crosslinkable compound may be added to the film hardness and fineness of the liquid crystal alignment film.

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

將本發明之液晶配向劑塗佈於基板上,焙燒後實施摩擦處理或光照射等之配向處理,或垂直配向用途等時無需配向處理下可作為液晶配向膜用。此時所使用之基板可為透明性較高之基板無特別限定,可使用玻璃基板,或丙烯酸基板、聚碳酸酯基板等之塑料基板。又,就步驟簡單化之觀點較佳為使用形成液晶驅動用之ITO電極等之基板。又,反射型之液晶顯示元 件可為僅單側基板使用矽電路板等不透明物,此時之電極可使用鋁等之反射光的材料。 The liquid crystal alignment agent of the present invention is applied onto a substrate, and after firing, it is subjected to an alignment treatment such as rubbing treatment or light irradiation, or a vertical alignment application or the like, and can be used as a liquid crystal alignment film without an alignment treatment. The substrate to be used at this time is not particularly limited as long as the substrate having high transparency, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. Further, in view of simplification of the steps, it is preferred to use a substrate on which an ITO electrode for liquid crystal driving or the like is formed. Also, reflective liquid crystal display element The opaque material such as a circuit board can be used for only one side substrate, and the electrode for reflecting light such as aluminum can be used as the electrode.

液晶配向劑之塗佈方法無特別限定,一般為工業上使用之網版印刷、膠版印刷、柔版印刷、噴墨印刷等之方法。其他之塗佈方法如,浸漬、輥塗、縫塗、旋塗等,可因應目的使用。 The coating method of the liquid crystal alignment agent is not particularly limited, and is generally a method such as screen printing, offset printing, flexographic printing, ink jet printing, or the like which is industrially used. Other coating methods such as dipping, roll coating, slit coating, spin coating, etc., can be used depending on the purpose.

將液晶配向劑塗佈於基板後之焙燒可藉由,熱板等之加熱手段以50至300℃,較佳以80至250℃進行,其次蒸發溶劑,可形成塗膜。焙燒後所形成之塗膜的厚度太厚時,不利於液晶顯示元件之消耗電力方面,太薄時會降低液晶顯示元件之信賴性,因此較佳為5至300nm,更佳為10至100nm。將液晶水平配向或傾斜配向時,可以摩擦或偏光紫外線照射等處理焙燒後之塗膜。 The baking of the liquid crystal alignment agent onto the substrate can be carried out by heating means such as a hot plate at 50 to 300 ° C, preferably 80 to 250 ° C, and then evaporating the solvent to form a coating film. When the thickness of the coating film formed after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when it is too thin, the reliability of the liquid crystal display element is lowered, so that it is preferably 5 to 300 nm, more preferably 10 to 100 nm. When the liquid crystal is aligned horizontally or obliquely, the coated film after baking may be treated by rubbing or polarized ultraviolet irradiation or the like.

本發明之液晶顯示元件為,藉由上述方法由本發明之液晶配向劑得附液晶配向膜之基板後,以已知之方法製作液晶單元所得的液晶顯示元件。 The liquid crystal display device of the present invention is a liquid crystal display device obtained by forming a liquid crystal cell by a known method from the liquid crystal alignment film of the present invention by the liquid crystal alignment agent of the present invention.

製作液晶單元之一例如,準備1對形成液晶配向膜之基板,將調距物散佈於單方基板之液晶配向膜上,以液晶配向膜面為內側之方式貼合另一方基板後,減壓注入液晶再密封之方法,或將液晶滴入散佈調距物之液晶配向膜面後貼合基板再密封之方法等。此時之調距物的厚度較佳為1至30μm,更佳為2至10μm。 For example, one pair of liquid crystal cells is prepared, and a pair of substrates for forming a liquid crystal alignment film are prepared, and a distance adjustment object is spread on a liquid crystal alignment film of a single substrate, and the other substrate is bonded so that the liquid crystal alignment film surface is inside, and then the pressure is injected. A method of resealing a liquid crystal, or a method of re-sealing a liquid crystal by dropping a liquid crystal into a liquid crystal alignment film surface on which a distance adjustment object is dispensed. The thickness of the pitch at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

如上述使用本發明之液晶配向劑製作的液晶顯示元件為,具有優良信賴性之物,適用於大畫面且高精細之液晶電視等。 The liquid crystal display element produced by using the liquid crystal alignment agent of the present invention as described above is excellent in reliability and is suitable for a large-screen and high-definition liquid crystal television.

實施例 Example

下面將舉實施例說明本發明,但本發明非限定以該例解釋。 The invention will now be illustrated by way of examples, but the invention is not limited by the examples.

實施例及比較例所使用之化合物的代號如下所述。 The symbols of the compounds used in the examples and comparative examples are as follows.

又,實施例及比較例所合成之聚醯胺酸(PAA)的內容、實施例及比較例所合成之可溶性聚醯亞胺(SPI)的內容、實施例及比較例所合成之聚醯胺酸酯(PAE)及聚醯胺的內容各自如表3、表4及表5所示。 Further, the contents of the polylysine (PAA) synthesized in the examples and the comparative examples, the contents of the soluble polyimine (SPI) synthesized in the examples and the comparative examples, and the polyamine synthesized in the examples and the comparative examples. The contents of the acid ester (PAE) and polyamine are shown in Table 3, Table 4 and Table 5, respectively.

另外實施例及比較例所調製之液晶配向劑(AL)的內容各自如表6及表7所示,實施例及比較例之液晶配向劑的配向劑印刷性、耐摩擦性、單元顯示特性評估結果如表8所示,使用實施例及比較例之液晶配向劑的液晶單元之特性評估結果如表9所示。 Further, the contents of the liquid crystal alignment agent (AL) prepared in the examples and the comparative examples are shown in Tables 6 and 7, and the alignment agent printability, the rubbing resistance, and the cell display characteristics of the liquid crystal alignment agents of the examples and the comparative examples were evaluated. The results are shown in Table 8, and the results of evaluation of the characteristics of the liquid crystal cells using the liquid crystal alignment agents of the examples and the comparative examples are shown in Table 9.

<四羧酸二酐> <tetracarboxylic dianhydride>

A-1:1,2,3,4-環丁烷四羧酸二酐 A-1:1,2,3,4-cyclobutane tetracarboxylic dianhydride

A-2:均苯四酸二酐 A-2: pyromellitic dianhydride

A-3:二環[3,3,0]辛烷-2,4,6,8-四羧酸二酐 A-3: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

A-4:2,3,5-三羧基環戊基乙酸-1,4:2,3-二酐 A-4: 2,3,5-tricarboxycyclopentyl acetic acid-1,4:2,3-dianhydride

A-5:1,2,3,4-環丁烷四羧酸二甲基酯 A-5: 1,2,3,4-cyclobutane tetracarboxylic acid dimethyl ester

A-6:己二醯氯化物 A-6: Dihexyl chloride

A-7:對苯二醯基氯化物 A-7: p-benzodioyl chloride

<二胺> <Diamine>

B-1:1,4-伸苯基二胺 B-1: 1,4-phenylenediamine

B-2:3-胺基苄基胺 B-2: 3-aminobenzylamine

B-3:1,3-伸苯基二胺 B-3: 1,3-phenylenediamine

B-4:4-十六烷氧基-1,3-二胺基苯 B-4: 4-hexadecyloxy-1,3-diaminobenzene

B-5:4-(反-4-戊基環己基)苯并醯胺-2’,4’-伸苯基二胺 B-5: 4-(trans-4-pentylcyclohexyl)benzoguanamine-2',4'-phenylene diamine

B-6:4-(反-4-戊基環己基)苯氧基-2’,4’-伸苯基二胺 B-6: 4-(trans-4-pentylcyclohexyl)phenoxy-2',4'-phenylene diamine

B-7:2,5-二胺基tert-丁氧基羰基胺基苯 B-7: 2,5-diamino tert-butoxycarbonylaminobenzene

B-8:2,4-二胺基tert-丁氧基羰基胺基苯 B-8: 2,4-diamino tert-butoxycarbonylaminobenzene

<縮合劑> <condenser>

DMT-MM:4-(4,6-二甲氧基-1,3,5-三嗪-2-基)4- 甲氧基嗎啉鎓氯化物n-水合物 DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)4- Methoxymorpholinium chloride n-hydrate

<有機溶劑> <organic solvent>

NMP:N-甲基-2-吡咯烷酮 NMP: N-methyl-2-pyrrolidone

GBL:γ-丁內酯 GBL: γ-butyrolactone

BC:丁基溶纖劑 BC: butyl cellosolve

THF:四氫呋喃 THF: tetrahydrofuran

DMF:N,N-二甲基甲醯胺 DMF: N,N-dimethylformamide

下面為本實施例所進行之評估方法。 The evaluation method performed in the following embodiment is as follows.

<分子量測定> <Molecular weight determination>

聚醯胺酸及聚醯亞胺之分子量為,使用GPC(常溫凝膠浸透色譜)裝置測定聚醯亞胺,算出聚乙二醇、聚環氧乙烷換算值之數平均分子量與重量平均分子量而得。 The molecular weight of polyglycine and polyimine is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight and weight average molecular weight of polyethylene glycol and polyethylene oxide are calculated. And got it.

GPC裝置:Shodex公司製(GPC-101) GPC device: manufactured by Shodex (GPC-101)

管柱:Shodex公司製(直列KD803、KD805) Pipe column: made by Shodex company (inline KD803, KD805)

管柱溫度:50℃ Column temperature: 50 ° C

溶離液:N,N-二甲基甲醯胺(添加劑用,溴化鋰單水合物(LiBr‧H2O)為30毫莫耳/L,磷酸無水結晶(o-磷酸)為30毫莫耳/L,四氫呋喃(THF)為10ml/L) Dissolution: N,N-dimethylformamide (for additive, lithium bromide monohydrate (LiBr‧H 2 O) is 30 mmol/L, anhydrous phosphate crystal (o-phosphoric acid) is 30 mmol/ L, tetrahydrofuran (THF) is 10ml / L)

流速:1.0ml/分 Flow rate: 1.0ml/min

檢量線製作用標準樣品:東曹公司製TSK標準聚環氧乙烷(分子量約900,000、150,000、100,000、 30,000,及聚合物拉波拉公司製聚乙二醇(分子量約12,000、4,000、1,000)。 Standard sample for the production of calibration lines: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight of about 900,000, 150,000, 100,000, 30,000, and polyethylene glycol (having a molecular weight of about 12,000, 4,000, 1,000) manufactured by Polymer Labola.

<醯亞胺化率測定> <醯Iminization rate determination>

以下述方法測定聚醯亞胺之醯亞胺化率。將聚醯亞胺粉末20mg放入NMR樣品管內,加入氘化二甲基亞碸(DMSO-d6,0.05%TMS混合品)0.53ml,使其完全溶解。使用日本電子丹達姆公司製NMR測定器(JNM-ECA500)測定該溶液的500MHz之質子NMR。 The ruthenium imidization ratio of the polyimine was measured by the following method. 20 mg of polyimine powder was placed in an NMR sample tube, and 0.53 ml of deuterated dimethyl hydrazine (DMSO-d 6 , 0.05% TMS mixture) was added to completely dissolve it. The 500 MHz proton NMR of this solution was measured using a NMR measuring instrument (JNM-ECA500) manufactured by JEOL Ltd., Japan.

醯亞胺化率係以下述式算出。又,式[1]所表示之未使用二胺的聚醯亞胺之醯亞胺化率係以下述式中之「聚醯胺酸聚合時的式[1]二胺之導入量」之值為0而算出。 The oxime imidization ratio was calculated by the following formula. Further, the ruthenium imidization ratio of the polyimine which is not used in the formula [1] is the value of the "introduction amount of the diamine of the formula [1] when the polyglycolic acid is polymerized" in the following formula. Calculated for 0.

醯亞胺化率(%)=(100-聚醯胺酸聚合時的式[1]=胺之導入量(mol%)×1/2)×α Ruthenium amination rate (%) = (Formula [1] in the polymerization of polyacrylic acid = introduction amount of amine (mol%) × 1/2) × α

式中α為,以來自醯亞胺化前後無變化之構造的質子為基準質子,使用該質子之峰積算值,與出現於9.5至10.0ppm附近來自醯胺酸之NH基的質子峰積算值以下述式求取。 In the formula, α is a proton measured from a proton having no change before and after imidization, and a peak product value of the proton is used, and a proton peak product value derived from an NH group derived from proline is present in the vicinity of 9.5 to 10.0 ppm. It is obtained by the following formula.

α=(1-α‧x/y) α=(1-α‧x/y)

上述式中,x為來自醯胺酸之NH基的質子峰積算值,y為基準質子之峰積算值,α為聚醯胺 酸(醯亞胺化率為0%)時相對於醯胺酸之NH基質子一個的基準質子之個數比例。 In the above formula, x is the proton peak product value of the NH group derived from proline, y is the peak product of the reference proton, and α is polyamine. The ratio of the number of reference protons relative to one of the NH protons of lysine when the acid (醯 imidization rate is 0%).

<製作液晶單元> <Making a liquid crystal cell>

將液晶配向劑旋塗於附透明電極之玻璃基板上,置於溫度80℃之熱板上乾燥70秒後,使用220℃之IR烤箱於氮環境下焙燒10分鐘,形成膜厚100nm之塗膜。使用輥徑120mm之摩擦裝置以棉布(吉川製YA-25C),於輥回轉數1000rpm、輥行進速度50mm/sec、擠入量0.4mm之條件下摩擦該塗膜面,得附液晶配向膜之基板。 The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C for 70 seconds, and then fired in a nitrogen oven at 220 ° C for 10 minutes in a nitrogen atmosphere to form a coating film having a film thickness of 100 nm. . Using a friction device with a roll diameter of 120 mm, the surface of the coating film was rubbed with a cotton cloth (YA-25C manufactured by Yoshikawa) at a roll rotation speed of 1000 rpm, a roll travel speed of 50 mm/sec, and a pushing amount of 0.4 mm to obtain a liquid crystal alignment film. Substrate.

準備該基板2枚,將6μm之調距物散佈於其中1枚之液晶配向膜面上,使用密封劑分配器將密封劑(住友化學股份公司製NX-1500T)印刷於其上方後,以液晶配向膜面面對面且摩擦方向直行之方式貼合另一枚基板,再硬化(假硬化:80℃ 30分鐘,本硬化:150℃ 1小時)密封劑製作空單元。以減壓注入法將液晶MLC-2003(美爾庫日本公司製)該空單元,密封注入口後,得扭轉向列液晶單元。 Two sheets of the substrate were prepared, and a pitch of 6 μm was spread on one of the liquid crystal alignment film surfaces, and a sealant (NX-1500T manufactured by Sumitomo Chemical Co., Ltd.) was printed thereon with a sealant dispenser, and liquid crystal was used. The other film is bonded to the surface of the alignment film and the rubbing direction is straight, and then hardened (false hardening: 80 ° C for 30 minutes, the present hardening: 150 ° C for 1 hour) to prepare an empty unit. The liquid crystal MLC-2003 (manufactured by Mercury Japan Co., Ltd.) was vacuum-filled to seal the injection port, and the nematic liquid crystal cell was twisted.

又,評估垂直配向(VA形態)用之液晶配向材料時係於未進行摩擦步驟下,以上述方法製作空單元,再注入液晶MLC-6608進行評估。 Further, when the liquid crystal alignment material for the vertical alignment (VA form) was evaluated, the empty cell was produced by the above method, and the liquid crystal MLC-6608 was injected for evaluation.

[樹脂印刷性試驗] [Resin printability test]

藉由洗淨之鉻板上使用配向膜印刷機(日本寫真印刷公司製「翁固斯」柔版印刷所調製之液晶配向處理劑,進行塗佈性試驗。將約1.0mL之液晶配向劑滴在網紋輥上,實施10次空運轉後,停止印刷機10分鐘,使印刷板乾燥。其後對1枚鉻基板進行印刷,將印刷後之基板置於70℃之熱板上5分鐘,進行塗膜之假乾燥,再觀察膜狀態,觀察時係以目視與50倍之光學顯微鏡(尼康公司製「ECLIPSE ME600」)進行,主要係觀察膜厚斑點及緣部之膜厚斑。 The coating property test was carried out by using a liquid crystal alignment treatment agent prepared by flexographic printing on a chrome plate on a cleaned chrome plate (manufactured by Nippon Photo Printing Co., Ltd.), and about 1.0 mL of the liquid crystal alignment agent was dropped thereon. After 10 empty runs were performed on the anilox roll, the printing machine was stopped for 10 minutes to dry the printing plate. Thereafter, one chromium substrate was printed, and the printed substrate was placed on a hot plate at 70 ° C for 5 minutes. The film was dried by a pseudo-drying, and the film state was observed. The observation was carried out by visual observation with a 50-fold optical microscope ("ECLIPSE ME600" manufactured by Nikon Corporation), mainly to observe film thickness spots and film thickness spots at the edges.

<預傾角測定> <Pretilt angle measurement>

同上述<液晶單元製作>以105℃加熱所得之液晶單元10分鐘後,進行預傾角測定。測定時係使用歐普特公司製Axo Scan繆勒矩陣光儀。 The liquid crystal cell obtained by heating the liquid crystal cell at 105 ° C for 10 minutes as described above was subjected to pretilt angle measurement. The Axo Scan Muller matrix light meter manufactured by Opt is used for the measurement.

<初期VHR(電壓保持率)測定> <Initial VHR (voltage retention rate) measurement>

60℃之溫度下於60μs間施加1V之電壓於以上述<製作液晶單元>所記載之方法製作的扭轉向列液晶單元上,測定166.7ms後之電壓,計算可保持多少電壓得電壓保持率,又,測定電壓保持率時係使用東陽技術公司製之VHR-1電壓保持率測定裝置。 A voltage of 1 V was applied at a temperature of 60 ° C for 60 μs to a twisted nematic liquid crystal cell fabricated by the method described in <Preparation of Liquid Crystal Cell>, and the voltage after 166.7 ms was measured to calculate how much voltage can be maintained. Further, when measuring the voltage holding ratio, a VHR-1 voltage holding ratio measuring device manufactured by Dongyang Technology Co., Ltd. was used.

<耐背光老化性> <Backlight aging resistance>

放置於40inch型液晶TV用背光組件上240小 時,以上述<初期VHR(電壓保持率)測定>之相同方法進行測定。 Placed on a 40-inch LCD TV backlight assembly 240 small In the same manner, the measurement was carried out in the same manner as the above <initial VHR (voltage holding ratio) measurement.

<高溫高濕試驗> <High temperature and high humidity test>

又放置於高溫高濕裝置內溫度70℃、濕度70%之環境下240小時,以上述<初期VHR(電壓保持率)測定>之相同方法進行測定。 Further, it was placed in an environment of a temperature of 70 ° C and a humidity of 70% for 240 hours in a high-temperature, high-humidity apparatus, and was measured in the same manner as the above-mentioned <initial VHR (voltage holding ratio) measurement.

<RDC(殘留DC電壓)測定> <RDC (Residual DC Voltage) Measurement>

23℃之溫度下將直流電壓以間隔0.1V由0V至1.0V之方式施加於以上述<製作液晶單元>所記載之方法製作的扭轉向列液晶單元上,使用光電變換裝置測定各電壓下之閃變震幅級數,再製作閃變震幅級數與施加電壓之檢量線。將單元接地放置5分鐘後,以1小時施加V50之交流電壓(亮度成為一半之電壓)、直流電壓5.0V後,測定僅直流電壓為0V瞬間之閃變震幅級數,再對照預先製作之檢量線估計RDC(該RDC之估計方法稱為閃變參考法)。 The DC voltage was applied to the twisted nematic liquid crystal cell produced by the method described in <Preparation of Liquid Crystal Cell> at a temperature of 23 ° C at a temperature of 0.1 V from 0 V to 1.0 V, and each voltage was measured using a photoelectric conversion device. The flicker amplitude series is used to make the sweep line of the flicker amplitude series and the applied voltage. After the unit was grounded for 5 minutes, an alternating voltage of V50 (voltage of half the brightness) and a direct current voltage of 5.0 V were applied for 1 hour, and then the magnitude of the flashing amplitude of only the direct current voltage of 0 V was measured, and then compared with the pre-made The calibration curve estimates the RDC (the estimation method for this RDC is called the flicker reference method).

<合成二胺> <Synthetic diamine>

實施例1 Example 1

合成2,5-二胺基tert-丁氧基羰基胺基苯[B-7] Synthesis of 2,5-diamino tert-butoxycarbonylaminobenzene [B-7]

Step 1:合成4-硝基2-tert丁氧基羰基胺基苯胺 Step 1: Synthesis of 4-nitro 2-tert-butoxycarbonylaminoaniline

以1L四口燒瓶測取4-硝基-1,2-伸苯基二胺50.0g(326.5mmol),加入THF500ml溶解後,氮環境下加熱至約60℃,再使用滴液漏斗以1小時緩緩滴入二碳酸tert丁酯71.3g(326.5mmol),回流4小時。 50.0 g (326.5 mmol) of 4-nitro-1,2-phenylenediamine was measured in a 1 L four-necked flask, dissolved in 500 ml of THF, heated to about 60 ° C in a nitrogen atmosphere, and then used in a dropping funnel for 1 hour. 71.3 g (326.5 mmol) of tert-butyl dicarbonate was slowly added dropwise and refluxed for 4 hours.

結束反應後,以回轉蒸發器濃縮反應溶液,再以乙酸乙酯:n-己烷之混合溶劑(體積比7:3)進行再結晶,得橘色固體62.0g(產率75%)。 After the completion of the reaction, the reaction solution was concentrated with a rotary evaporator, and recrystallized from ethyl acetate: n-hexane (yield: 7:3) to give 62.0 g (yield: 75%) of an orange solid.

Step 2:合成[B-7] Step 2: Synthesis [B-7]

以1L四口燒瓶秤取2-tert丁氧基羰基胺基-5-硝基苯胺60.0g(236.9mmol)、10wt%鈀碳6.0g後,加入THF500ml,進行減壓脫氣及氫取代,室溫下反應24小時。 60.0 g (236.9 mmol) of 2-tert-butoxycarbonylamino-5-nitroaniline and 6.0 g of 10 wt% palladium carbon were weighed in a 1 L four-necked flask, and then 500 ml of THF was added thereto to carry out vacuum degassing and hydrogen substitution. The reaction was allowed to proceed for 24 hours.

結束反應後,以PTFE製膜濾器去除鈀碳,再以回轉蒸發器濃縮濾液,其後以乙酸乙酯與n-己烷之混 合溶劑(體積比5:5)進行再結晶,得目的之淡紅色固體狀之二胺50.2g(產率95%)。以分子內氫原子之核磁共振光譜的1H-NMR光譜確認其構造,所得測定數據如下所示。 After the completion of the reaction, the palladium carbon was removed by a PTFE membrane filter, and the filtrate was concentrated by a rotary evaporator, followed by recrystallization from a mixed solvent of ethyl acetate and n-hexane (volume ratio: 5:5). 50.2 g (yield 95%) of a diamine as a red solid. The structure was confirmed by 1 H-NMR spectrum of a nuclear magnetic resonance spectrum of intramolecular hydrogen atoms, and the obtained measurement data are shown below.

1H-NMR(400MHz,[D6]-DMSO)δ:6.91-6.89(d,1H)、6.12-6.09(d-d,2H)、5.95(s-br,1H)、3.75(s-br,2H)、5.95(s-br,2H)、3.53(s-br,2H)、1.49(s,9H)。 1 H-NMR (400 MHz, [D 6 ]-DMSO) δ: 6.91-6.89 (d, 1H), 6.12-6.09 (dd, 2H), 5.95 (s-br, 1H), 3.75 (s-br, 2H) ), 5.95 (s-br, 2H), 3.53 (s-br, 2H), 1.49 (s, 9H).

實施例2 Example 2

合成2,4-二胺基-2-tert-丁氧基羰基胺基苯[B-8] Synthesis of 2,4-diamino-2-tert-butoxycarbonylaminobenzene [B-8]

Step 1:合成2,4-二硝基tert丁氧基羰基胺基苯 Step 1: Synthesis of 2,4-dinitrotert-butoxycarbonylaminobenzene

以1L四口燒瓶測取氫化鈉(Pure:50%)22.8g(約273.0mmol),加入DMF500ml後,氮環境下冷卻至0℃,再緩緩滴入2,4-二硝基苯胺50.0g(273.0mmol)之 DMF溶液反應1小時,使用滴液漏斗以1小時緩緩滴入二碳酸tert丁酯59.6g(273.0mmol),室溫下反應2小時。 22.8 g (about 273.0 mmol) of sodium hydride (Pure: 50%) was measured in a 1 L four-necked flask, and 500 ml of DMF was added thereto, and then cooled to 0 ° C under a nitrogen atmosphere, and then 2,4-dinitroaniline 50.0 g was slowly added dropwise. (273.0mmol) The DMF solution was reacted for 1 hour, and 59.6 g (273.0 mmol) of tert-butyl dicarbonate was gradually added dropwise over 1 hour using a dropping funnel, and the mixture was reacted at room temperature for 2 hours.

結束反應後,加入離子交換水500ml攪拌下析出固體,再過濾回收固體,以甲醇洗淨數次後,以乙酸乙酯與n-己烷之混合溶劑(體積比5:5)進行再結晶,得淡黃色之固體60.3g(產率78%)。 After completion of the reaction, 500 ml of ion-exchanged water was added thereto to precipitate a solid with stirring, and the solid was collected by filtration, washed with methanol several times, and then recrystallized from a mixed solvent of ethyl acetate and n-hexane (volume ratio: 5:5). A pale yellow solid was obtained (yield: 78%).

Step 2:合成[B-8] Step 2: Synthesis [B-8]

以1L四口燒瓶秤取2,4-二硝基tert丁氧基羰基胺基苯60.0g(211.8mmol)、10wt%鈀碳6.0g後,加入THF500ml進行減壓脫氣及氫取代,室溫下反應24小時。 60.0 g (211.8 mmol) of 2,4-dinitrotert-butoxycarbonylaminobenzene and 6.0 g of 10 wt% palladium carbon were weighed in a 1 L four-necked flask, and then 500 ml of THF was added thereto to carry out vacuum degassing and hydrogen substitution at room temperature. The reaction was carried out for 24 hours.

反應結束後,以PTFE製膜濾器去除鈀碳,再以回轉蒸發器濃縮濾液,其後以乙酸乙酯與n-己烷之混合溶劑(體積比3:7)進行再結晶,得目的之乳白色固體狀二胺45.9g(產率97%)。以分子內氫原子之核磁共振光譜的1H-NMR確認其構造,測定數據如下所示。 After the completion of the reaction, the palladium carbon was removed by a membrane filter made of PTFE, and the filtrate was concentrated by a rotary evaporator, followed by recrystallization from a mixed solvent of ethyl acetate and n-hexane (volume ratio: 3:7) to obtain a desired white color. 45.9 g of solid diamine (yield 97%). The structure was confirmed by 1 H-NMR of a nuclear magnetic resonance spectrum of intramolecular hydrogen atoms, and the measurement data are shown below.

1H-NMR(400MHz,[D6]-DMSO)δ:7.07(s-br,1H)、6.68(d,1H)、6.67-6.63(d-d、1H)、6.35-6.32(d-d,1H)、3.42(s-br,2H)、3.12(s-br,2H)、1.50(s,9H)。 1 H-NMR (400 MHz, [D 6 ]-DMSO) δ: 7.07 (s-br, 1H), 6.68 (d, 1H), 6.67-6.63 (dd, 1H), 6.35-6.32 (dd, 1H), 3.42 (s-br, 2H), 3.12 (s-br, 2H), 1.50 (s, 9H).

實施例3 Example 3

聚合聚醯胺酸[PAA-1:A-1/B-7]與調製配向劑 [AL-1] Polymerized polylysine [PAA-1: A-1/B-7] and preparation of alignment agent [AL-1]

以備有氮導入管與機械攪拌器之50ml四口燒瓶測取B-7 3.35g(15.00mmol),加入NMP 34.8g溶解後,氮環境下冷卻至約10℃,再少許分次加入A-1 28.5g(14.60mmol),返回室溫下反應6小時,得15質量%之聚醯胺酸溶液[PAA-1]。 B-7 3.35g (15.00mmol) was prepared in a 50ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. After dissolved in N4.8 (34.8g), it was cooled to about 10 ° C in a nitrogen atmosphere, and then added to A- 1 28.5 g (14.60 mmol), and returned to room temperature for 6 hours to obtain a 15 mass% polylysine solution [PAA-1].

所得之PAA-1之數平均分子量為11,300,重量平均分子量為24,500。 The obtained PAA-1 had an average molecular weight of 11,300 and a weight average molecular weight of 24,500.

以備有攪拌子之50ml三角燒瓶秤取該聚醯胺酸溶液10.0g,加入NMP 7.5g及BCS 7.5g後,室溫下攪拌30分鐘,得PAA-1 6.0質量%、NMP 64質量%、BCS 30質量%之配向劑[AL-1]。 10.0 g of the polyaminic acid solution was weighed in a 50 ml Erlenmeyer flask equipped with a stirrer, and 7.5 g of NMP and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 30 minutes to obtain PAA-1 6.0% by mass and NMP 64% by mass. BCS 30% by mass of the alignment agent [AL-1].

實施例4 Example 4

合成可溶性聚醯亞胺[SPI-1:A-1/B-7]與調製配向劑[AL-2] Synthesis of soluble polyimine [SPI-1: A-1/B-7] and preparation of alignment agent [AL-2]

以備有攪拌子之100ml三角燒瓶測取實施例3所得之聚醯胺酸溶液[PPA-1]30.0g,加入NMP34.3g、乙酸酐3.32g、吡啶1.37g後,室溫下攪拌30分鐘,再於50℃下攪拌反應3小時。結束反應後緩緩注入240ml之甲醇內析出聚合物,攪拌30分鐘後,過濾回收固體。以甲醇充分洗淨所得之固體後,於100℃下真空乾燥,得聚醯亞胺[SPI-1]。該聚醯亞胺之數平均分子量為10,300,重量平均分子量為22,600,醯 亞胺化率為82%。 30.0 g of the polyaminic acid solution [PPA-1] obtained in Example 3 was measured in a 100 ml Erlenmeyer flask equipped with a stirrer, and after adding NMP 34.3 g, acetic anhydride 3.32 g, and pyridine 1.37 g, the mixture was stirred at room temperature for 30 minutes. The reaction was further stirred at 50 ° C for 3 hours. After completion of the reaction, the polymer was gradually poured into 240 ml of methanol, and the mixture was stirred for 30 minutes, and then the solid was collected by filtration. The obtained solid was sufficiently washed with methanol, and then dried under vacuum at 100 ° C to obtain a polyimine [SPI-1]. The polyimine has a number average molecular weight of 10,300 and a weight average molecular weight of 22,600. The imidization ratio was 82%.

以備有攪拌子之50ml三角燒瓶測取SPI-1 2.00g,加入GBL 18.0g後50℃下攪拌24小時使其溶解,確認完全溶解後,加入GBL 3.33g、BCS 10.0g,室溫下攪拌30分鐘,得SPI-1 6.0質量%、GBL 64質量%、BCS 30質量%之配向劑[A1-2]。 SPI-1 2.00g was measured in a 50ml Erlenmeyer flask equipped with a stirrer. After adding GBL 18.0g, stir at 50 °C for 24 hours to dissolve. After confirming complete dissolution, add GBL 3.33g, BCS 10.0g, and stir at room temperature. In 30 minutes, an aligning agent [A1-2] having SPI-1 6.0% by mass, GBL 64% by mass, and BCS 30% by mass was obtained.

實施例5 Example 5

聚合聚醯胺酸[PAA-2:A-1/B-8]與調製配向劑[AL-3] Polymeric polyaminic acid [PAA-2: A-1/B-8] and preparation of alignment agent [AL-3]

以備有氮導入管與機械攪拌器之50ml四口燒瓶測取B-8 3.35g(15.00mmol),加入NMP 34.8g溶解後,氮環境下冷卻至約10℃,再少許分次加入A-1 2.85g(14.60mmol),返回室溫後反應6小時得15質量%之聚醯胺酸溶液[PAA-2]。 B-8 3.35g (15.00mmol) was prepared in a 50ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. After dissolving N4.8 34.8g, it was cooled to about 10 ° C in a nitrogen atmosphere, and then added to A- 1 2.85 g (14.60 mmol), and returned to room temperature, and reacted for 6 hours to obtain 15% by mass of a polyaminic acid solution [PAA-2].

所得之PAA-2之數平均分子量為13,900,重量平均分子量為28,300。 The obtained PAA-2 had a number average molecular weight of 13,900 and a weight average molecular weight of 28,300.

以備有攪拌子之50ml三角燒瓶秤取該聚醯胺酸溶液10.0g,加入NMP 7.5g、BCS 7.5g後,室溫下攪拌30分鐘,得PAA-1為6.0質量%、NMP為64質量%、BCS為30質量%之配向劑[AL-3]。 10.0 g of the polyaminic acid solution was weighed in a 50 ml Erlenmeyer flask equipped with a stirrer, and 7.5 g of NMP and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 30 minutes to obtain a PAA-1 of 6.0% by mass and an NMP of 64 mass. % and BCS are 30% by mass of an alignment agent [AL-3].

實施例6 Example 6

合成可溶性聚醯亞胺[SPI-2:A-1/B-8]與調製配 向劑[AL-4] Synthesis of soluble polyimine [SPI-2: A-1/B-8] and modulation Agent [AL-4]

以備有攪拌子之100ml三角燒瓶測取實施例5所得之聚醯胺酸溶液[PAA-2]30.0g,加入NMP34.3g、乙醯酐3.32g、吡啶1.37g後,室溫下攪拌30分鐘,再於50℃下攪拌反應3小時。結束反應後,緩緩注入240ml之甲醯內析出聚合物,攪拌30分鐘後,過濾回收固體。以甲醯充分洗淨所得之固體後,100℃下真空乾燥得聚醯亞胺[SPI-2]。該聚醯亞胺之數平均分子量為12,800,重量平均分子量為26,600,醯亞胺化率為85%。 30.0 g of the polyaminic acid solution [PAA-2] obtained in Example 5 was measured in a 100 ml Erlenmeyer flask equipped with a stirrer, and 3,3 g of NMP, 3.32 g of acetaldehyde anhydride, and 1.37 g of pyridine were added, followed by stirring at room temperature. After a minute, the reaction was further stirred at 50 ° C for 3 hours. After the completion of the reaction, the polymer was gradually poured into 240 ml of formazan, and after stirring for 30 minutes, the solid was collected by filtration. The obtained solid was sufficiently washed with formazan, and dried under vacuum at 100 ° C to obtain polyimine [SPI-2]. The polyimine had a number average molecular weight of 12,800, a weight average molecular weight of 26,600, and a ruthenium iodide ratio of 85%.

以備有攪拌子之50ml三角燒瓶測取SPI-2 2.00g,加入GBL 18.0g後50℃下攪拌24小時使其溶解,確認完全溶解後,加入GBL 3.33g、BCS 10.0g,室溫下攪拌30分鐘,得SPI-1為6.0質量%、GBL為64質量%、BCS為30質量%之配向劑[AL-4]。 SPI-2 2.00g was measured in a 50ml Erlenmeyer flask equipped with a stirrer. After adding GBL 18.0g, it was stirred at 50 °C for 24 hours to dissolve. After confirming complete dissolution, add GBL 3.33g, BCS 10.0g, and stir at room temperature. After 30 minutes, an aligning agent [AL-4] having an SPI-1 of 6.0% by mass, a GBL of 64% by mass, and a BCS of 30% by mass was obtained.

實施例7 Example 7

聚合聚醯胺酸[PAA-3:A-2/B-7]與調製配向劑[AL-5] Polymeric polyamine acid [PAA-3: A-2/B-7] and preparation of alignment agent [AL-5]

以備有氮導入管與機械攪拌器之50ml四口燒瓶測取B-7 2.33g(6.00mmol),加入NMP 14.5g溶解後,氮環境下冷卻至約10℃,再少許分次加入A-2 1.22g(5.58mmol),返回室溫下反應6小時得15質量 %之聚醯胺酸[PAA-3]。 B-7 2.33g (6.00mmol) was prepared in a 50ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. After dissolved in NMP 14.5g, it was cooled to about 10 ° C in a nitrogen atmosphere, and then added to A- in small portions. 2 1.22g (5.58mmol), return to room temperature for 6 hours to get 15 mass % polylysine [PAA-3].

所得之PAA-3之數平均分子量為9,600,重量平均分子量為20,100。 The obtained PAA-3 had an average number average molecular weight of 9,600 and a weight average molecular weight of 20,100.

以備有攪拌子之50ml三角燒瓶秤取該聚醯胺酸溶液15.0g,加入NMP 11.3g、BCS 11.3g後,室溫下攪拌30分鐘,得PAA-3為6.0質量%、NMP為64質量%、BCS為30質量%之配向劑[AL-5]。 15.0 g of the polyaminic acid solution was weighed in a 50 ml Erlenmeyer flask equipped with a stirrer, and 11.3 g of NMP and 11.3 g of BCS were added, and the mixture was stirred at room temperature for 30 minutes to obtain a PAA-3 of 6.0% by mass and an NMP of 64 mass. % and BCS are 30% by mass of an alignment agent [AL-5].

實施例8 Example 8

聚合聚醯胺酸[PAA-4:A-2/B-8]與調製配向劑[AL-6] Polymeric polyamine acid [PAA-4: A-2/B-8] and preparation of alignment agent [AL-6]

以備有氮導入管與機械攪拌器之50ml四口燒瓶測取B-8 2.33g(6.00mmol),加入NMP 14.5g溶解後,氮環境下冷卻至約10℃,再少許分次加入A-2 1.22g(5.58mmol),返回室溫下反應6小時得15質量%之聚醯胺酸溶液[PAA-4]。 B-8 2.33g (6.00mmol) was prepared in a 50ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. After dissolved in NMP 14.5g, it was cooled to about 10 ° C in a nitrogen atmosphere, and then added to A- in small portions. 2 1.22 g (5.58 mmol), and returned to room temperature for 6 hours to obtain 15% by mass of a polyaminic acid solution [PAA-4].

所得之PAA-4之數平均分子量為9,200,重量平均分子量為19,900。 The obtained PAA-4 had an average number average molecular weight of 9,200 and a weight average molecular weight of 19,900.

以備有攪拌子之50ml三角燒瓶測取該聚醯胺酸溶液15.0g,加入NMP 11.3g、BCS 11.3g後,室溫下攪拌30分鐘,得PAA-3為6.0質量%、NMP為64質量%、BCS為30質量%之配向劑[AL-6]。 15.0 g of the polyaminic acid solution was measured in a 50 ml Erlenmeyer flask equipped with a stirrer, and 11.3 g of NMP and 11.3 g of BCS were added, and the mixture was stirred at room temperature for 30 minutes to obtain a PAA-3 of 6.0% by mass and an NMP of 64 mass. % and BCS are 30% by mass of an alignment agent [AL-6].

實施例9 Example 9

合成可溶性聚醯亞胺[SPI-3:A-1、A-2(30)/B-2、B-7(40)、B-4(20)]與調製配向劑[AL-7] Synthesis of soluble polyimine [SPI-3: A-1, A-2 (30) / B-2, B-7 (40), B-4 (20)] and modulation alignment agent [AL-7]

以備有氮導入管與機械攪拌器之50ml四口燒瓶測取B-2 0.92g(7.50mmol)、B-7 2.23g(10.00mmol)、B-4 1.74g(5.00mmol),加入NMP 39.5g溶解後,氮環境下冷卻至約10℃,再少許分次加入A-2 1.64g(7.50mmol),返回室溫下反應30分鐘,再加入A-1 3.36g(17.13mmol),室溫下反應16小時得20質量%之聚醯胺酸溶液[PAA-6]。 B-2 0.92g (7.50mmol), B-7 2.23g (10.00mmol), B-4 1.74g (5.00mmol), and NMP 39.5 were added to a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. After g is dissolved, it is cooled to about 10 ° C under nitrogen atmosphere, and then A-2 1.64 g (7.50 mmol) is added in portions, and the reaction is returned to room temperature for 30 minutes, and then A-1 3.36 g (17.13 mmol) is added, room temperature. The reaction was carried out for 16 hours to obtain 20% by mass of a polyaminic acid solution [PAA-6].

所得之PAA-6之數平均分子量為12,800,重量平均分子量為29,600。 The obtained PAA-6 had a number average molecular weight of 12,800 and a weight average molecular weight of 29,600.

以備有攪拌子之100ml三角燒瓶測取前述所得之聚醯胺酸溶液30.0g,加入NMR 45.0g、乙酸乙酯4.39g(43.00mmol)、吡啶1.87g(23.65mmol)後,室溫下攪拌30分鐘,再於50℃下攪拌反應3小時。結束反應後,緩緩注入200ml之甲醇內析出聚合物,攪拌30分鐘後,過濾回收固體。以甲醇充分洗淨所得之固體後,100℃下真空乾燥,得聚醯亞胺[SPI-3]。該聚醯亞胺之數平均分子量為11,200,重量平均分子量為24,300,醯亞胺化率為92%。 30.0 g of the polyamic acid solution obtained above was measured in a 100 ml Erlenmeyer flask equipped with a stir bar, and NMR 45.0 g, ethyl acetate 4.39 g (43.00 mmol), and pyridine 1.87 g (23.65 mmol) were added, followed by stirring at room temperature. After 30 minutes, the reaction was further stirred at 50 ° C for 3 hours. After completion of the reaction, the polymer was gradually poured into 200 ml of methanol, and the mixture was stirred for 30 minutes, and then the solid was collected by filtration. The obtained solid was sufficiently washed with methanol, and dried under vacuum at 100 ° C to obtain a polyimine [SPI-3]. The polyimine had a number average molecular weight of 11,200, a weight average molecular weight of 24,300, and a ruthenium iodide ratio of 92%.

以備有攪拌子之50ml三角燒瓶測取SPI-3 2.00g,加入GBL 18.0g後50℃下攪拌24小時使其溶解,確認完全溶解後,加入GBL 3.33g、BCS 10.0g,室溫下攪拌30分鐘,得SPI-3為6.0質量 %、GBL為64質量%、BCS為30質量%之配向劑[AL-7]。 SPI-3 2.00g was measured in a 50ml Erlenmeyer flask equipped with a stirrer. After adding GBL 18.0g, it was stirred at 50 °C for 24 hours to dissolve. After confirming complete dissolution, add GBL 3.33g, BCS 10.0g, and stir at room temperature. 30 minutes, SPI-3 is 6.0 quality %, GBL is 64% by mass, and BCS is 30% by mass of an alignment agent [AL-7].

實施例10 Example 10

合成可溶性聚醯亞胺[SPI-4:A-1、A-2(30)/B-2、B-8(40)、B-4(20)]與調製配向劑[AL-8] Synthesis of soluble polyimine [SPI-4: A-1, A-2 (30) / B-2, B-8 (40), B-4 (20)] and modulation alignment agent [AL-8]

直接以B-8取代實施例9之B-7進行相同操作,得20質量%之聚醯胺酸溶液。 The same operation was carried out by directly substituting B-8 for B-7 of Example 9, to obtain a 20% by mass solution of polyamine.

所得之聚醯胺酸之數平均分子量為10,600,重量平均分子量為26,600。 The obtained polyamic acid had a number average molecular weight of 10,600 and a weight average molecular weight of 26,600.

使用PAA-6進行與實施例10相同之操作,得聚醯亞胺[SPI-4]及SPI-4為6.0質量%、GBL為64質量%、BCS為30質量%之配向劑[AL-8]。該聚醯亞胺之數平均分子量為9,900,重量平均分子量為21,300,醯亞胺化率為90%。 The same operation as in Example 10 was carried out using PAA-6 to obtain an alignment agent [AL-8] having a polyamidene [SPI-4] and SPI-4 of 6.0% by mass, a GBL of 64% by mass, and a BCS of 30% by mass. ]. The polyimine had a number average molecular weight of 9,900, a weight average molecular weight of 21,300, and a ruthenium iodide ratio of 90%.

實施例11 Example 11

合成可溶性聚醯亞胺[SPI-5:A-1、A-2(30)/B-2、B-7(40)、B-5(15)]與調製配向劑[A1-9] Synthesis of soluble polyimine [SPI-5: A-1, A-2 (30) / B-2, B-7 (40), B-5 (15)] and modulation alignment agent [A1-9]

以備有氮導入管與機械攪拌器之50ml四口燒瓶測取B-2 1.10g(9.00mmol)、B-7 1.78g(8.00mmol)、B-5 1.22g(3.00mmol),加入NMP 32.3g溶解後,氮環境下冷卻至約10℃,再少許分次加入A-2 1.30g(6.00mmol),返回室溫下反應30分鐘,再加入 A-1 2.67g(13.60mmol),室溫下反應16小時得20質量%之聚醯胺酸溶液。 B-2 1.10 g (9.00 mmol), B-7 1.78 g (8.00 mmol), B-5 1.22 g (3.00 mmol), and NMP 32.3 were added to a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. After g is dissolved, it is cooled to about 10 ° C in a nitrogen atmosphere, and then added to A-2 1.30 g (6.00 mmol) in small portions, and returned to room temperature for 30 minutes, and then added. A-1 2.67 g (13.60 mmol) was reacted at room temperature for 16 hours to obtain a 20 mass% polyamine acid solution.

所得之聚醯胺酸之數平均分子量為10,900,重量平均分子量為32,600。 The obtained polyamic acid had a number average molecular weight of 10,900 and a weight average molecular weight of 32,600.

以備有攪拌子之100ml三角燒瓶測取前述所得之聚醯胺酸溶液[PAA-7]30.0g,加入NMP 45.0g、乙酸酐4.39g(43.00mmol)、吡啶1.87g(23.65mmol)後,室溫下攪拌30分鐘,再於50℃下攪拌反應3小時。結束反應後,緩緩注入200ml之甲醇內析出聚合物,攪拌30分鐘後,過濾回收固體。以甲醇充分洗淨所得之固體後,100℃下真空乾燥得聚醯亞胺[SPI-5]。該聚醯亞胺之數平均分子量為10,200,重量平均分子量為27,300,醯亞胺化率為94%。 30.0 g of the polyamic acid solution [PAA-7] obtained above was measured in a 100 ml Erlenmeyer flask equipped with a stirrer, and after adding 45.0 g of NMP, 4.39 g (43.00 mmol) of acetic anhydride, and 1.87 g (23.65 mmol) of pyridine, The mixture was stirred at room temperature for 30 minutes, and further stirred at 50 ° C for 3 hours. After completion of the reaction, the polymer was gradually poured into 200 ml of methanol, and the mixture was stirred for 30 minutes, and then the solid was collected by filtration. The obtained solid was sufficiently washed with methanol, and dried under vacuum at 100 ° C to obtain a polyimine [SPI-5]. The polyimine had a number average molecular weight of 10,200, a weight average molecular weight of 27,300, and a ruthenium iodide ratio of 94%.

以備有攪拌子之50ml三角燒瓶測取SPI-5 2.00g,加入GBL 18.0g後50℃下攪拌24小時使其溶解,確認完全溶解後,加入GBL 3.33g、BCS 10.0g,室溫下攪拌30分鐘,得SPI-5為6.0質量%、GBL為64質量%、BCS為30質量%之配向劑[AL-9]。 SPI-5 2.00g was measured in a 50ml Erlenmeyer flask equipped with a stirrer. After adding GBL 18.0g, it was stirred at 50 °C for 24 hours to dissolve. After confirming complete dissolution, add GBL 3.33g, BCS 10.0g, and stir at room temperature. For 30 minutes, an aligning agent [AL-9] having an SPI-5 of 6.0% by mass, a GBL of 64% by mass, and a BCS of 30% by mass was obtained.

實施例12 Example 12

合成可溶性聚醯亞胺[SPI-6:A-1、A-3(50)/B-1、B-7(40)、B-6(20)]與調製配向劑[A1-10] Synthesis of soluble polyimine [SPI-6: A-1, A-3 (50) / B-1, B-7 (40), B-6 (20)] and preparation of alignment agent [A1-10]

以備有氮導入管與機械攪拌器之50ml四口燒瓶測取B-1 0.65g(6.00mmol)、B-7 1.34g(6.00mmol)、B-6 1.14g(3.00mmol),加入NMP 25.0g溶解後,室溫下加入A-3 1.88g(7.50mmol),氮環境80℃下反應4小時,再加入A-1 1.44g(7.35mmol),室溫下反應16小時,得20質量%之聚醯胺酸溶液。 B-1 0.65g (6.00mmol), B-7 1.34g (6.00mmol), B-6 1.14g (3.00mmol), and NMP 25.0 were added to a 50ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. After g was dissolved, 1.38 g (7.50 mmol) of A-3 was added at room temperature, and the reaction was carried out for 4 hours at 80 ° C in a nitrogen atmosphere, and then 1.1 g (7.35 mmol) of A-1 was added thereto, and the mixture was reacted at room temperature for 16 hours to obtain 20% by mass. Poly-proline solution.

所得之聚醯胺酸之數平均分子量為15,900,重量平均分子量為42,800。 The obtained polyamic acid had a number average molecular weight of 15,900 and a weight average molecular weight of 42,800.

以備有攪拌子之100ml三角燒瓶測取前述所得之聚醯胺酸溶液30.0g,加入NMP 55.7g、乙酸酐6.71g(65.74mmol)、吡啶5.20g(65.74mmol)後,室溫下攪拌30分鐘,再於90℃下攪拌反應2.5小時,結束反應後,緩緩注入200ml之甲醇內析出聚合物,攪拌30分鐘後,過濾回收固體。以甲醇充分洗淨所得之固體後,100℃下真空乾燥得聚醯亞胺[SPI-6]。該聚醯亞胺之數平均分子量為14,300,重量平均分子量為33,300,醯亞胺化率為69%。 30.0 g of the polyamic acid solution obtained above was measured in a 100 ml Erlenmeyer flask equipped with a stirrer, and 55.7 g of NMP, 6.71 g (65.74 mmol) of acetic anhydride, and 5.20 g (65.74 mmol) of pyridine were added, followed by stirring at room temperature. After a minute, the reaction was further stirred at 90 ° C for 2.5 hours. After the completion of the reaction, the polymer was gradually poured into 200 ml of methanol, and the mixture was stirred for 30 minutes, and then the solid was collected by filtration. The obtained solid was sufficiently washed with methanol, and dried under vacuum at 100 ° C to obtain polyimine [SPI-6]. The polyimine had a number average molecular weight of 14,300, a weight average molecular weight of 33,300, and a ruthenium iodide ratio of 69%.

以備有攪拌子之50ml三角燒瓶測取SPI-6 2.00g,加入NMP 18.0g後50℃下攪拌24小時使其溶解,確認完全溶解後,加入NMP 3.33g、BCS 10.0g,室溫下攪拌30分鐘,得SPI-6為6.0質量%、NMP為64質量%、BCS為30質量%之配向劑[AL-10]。 2.00 g of SPI-6 was measured in a 50 ml Erlenmeyer flask equipped with a stirrer. After adding N8.0 18.0 g, it was stirred at 50 ° C for 24 hours to dissolve. After confirming complete dissolution, NMP 3.33 g, BCS 10.0 g were added, and stirred at room temperature. After 30 minutes, an aligning agent [AL-10] having 6.0% by mass of SPI-6, 64% by mass of NMP, and 30% by mass of BCS was obtained.

實施例13 Example 13

合成可溶性聚醯亞胺[SPI-7:A-1、A-4(50)/B-1、B-7(40)、B-6(20)]與調製配向劑[A1-11] Synthesis of soluble polyimine [SPI-7: A-1, A-4 (50) / B-1, B-7 (40), B-6 (20)] and modulation alignment agent [A1-11]

以備有氮導入管與機械攪拌器之50ml四口燒瓶測取B-1 0.65g(6.00mmol)、B-7 1.34g(10.00mmol)、B-6 1.14(5.00mmol),加入NMP 25.0g溶解後,氮環境下冷卻至約10℃,再少許分次加入A-4 1.68g(7.50mmol),回復室溫後再反應30分鐘,再加入A-1 1.44g(7.35mmol),室溫下反應16小時得酸溶液。 B-1 0.65g (6.00mmol), B-7 1.34g (10.00mmol), B-6 1.14 (5.00mmol), and NMP 25.0g were added to a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. After dissolving, it was cooled to about 10 ° C under nitrogen atmosphere, and then added to A-4 1.68 g (7.50 mmol) in small portions. After returning to room temperature, the reaction was further carried out for 30 minutes, and then A-1 1.44 g (7.35 mmol) was added thereto at room temperature. The reaction was carried out for 16 hours to obtain an acid solution.

所得之聚醯胺酸之數平均分子量為13,800,重量平均分子量為39,800。 The obtained polyamic acid had a number average molecular weight of 13,800 and a weight average molecular weight of 39,800.

以備有攪拌子之100ml三角燒瓶測取前述所得之聚醯胺酸溶液30.0g,加入NMP 55.7g、乙酸酐6.71g(65.74mmol)、吡啶5.20g(65.74mmol)後,室溫下攪拌30分鐘,再於90℃下攪拌反應3小時。結束反應後,緩緩注入200ml之甲醇內析出聚合物,攪拌30分鐘後過濾回收固體。以甲醇充分洗淨所得之固體後,100℃下真空乾燥得[SPI-7]。該聚醯亞胺之數平均分子量為14,300,重量平均分子量為33,300,醯亞胺化率為62%。 30.0 g of the polyamic acid solution obtained above was measured in a 100 ml Erlenmeyer flask equipped with a stirrer, and 55.7 g of NMP, 6.71 g (65.74 mmol) of acetic anhydride, and 5.20 g (65.74 mmol) of pyridine were added, followed by stirring at room temperature. After a minute, the reaction was further stirred at 90 ° C for 3 hours. After completion of the reaction, the polymer was gradually poured into 200 ml of methanol, and the mixture was stirred for 30 minutes, and then the solid was collected by filtration. The obtained solid was sufficiently washed with methanol, and dried under vacuum at 100 ° C to obtain [SPI-7]. The polyimine had a number average molecular weight of 14,300, a weight average molecular weight of 33,300, and a ruthenium iodide ratio of 62%.

以備有攪拌子之50ml三角燒瓶測取SPI-7 2.00g,加入NMP 18.0g後50℃下攪拌24小時使其溶解,確認完全溶解後,加入NMP 3.33g、BCS 10.0g,室溫下攪拌30分鐘,得SPI-7為6.0質量%、NMP為64質量%、BCS為30質量%之配向劑[AL-11]。 2.00 g of SPI-7 was measured in a 50 ml Erlenmeyer flask equipped with a stirrer, and 18.0 g of NMP was added, and the mixture was stirred at 50 ° C for 24 hours to be dissolved. After confirming complete dissolution, NMP 3.33 g, BCS was added. 10.0 g was stirred at room temperature for 30 minutes to obtain an alignment agent [AL-11] having SPI-7 of 6.0% by mass, NMP of 64% by mass, and BCS of 30% by mass.

實施例14 Example 14

合成聚醯胺酸酯[PAE-1:A-5/B-1、B-7(40)、B-4(10)]與調製配向劑[AL-12] Synthesis of polyamidomate [PAE-1: A-5/B-1, B-7 (40), B-4 (10)] and preparation of alignment agent [AL-12]

將A-5 2.96g(11.40mmol)、二胺成分之B-1 0.52g(4.80mmol)、B-7 1.07g(4.80mmol)、B-4 0.41g(1.20mmol)、NMP 36.5g、三乙基胺0.60g(5.90mmol)加入備有氮導入管與攪拌子之100ml四口燒瓶內,冷卻至約10℃後加入DMT-MM 9.96g(36.00mmol),返回室溫後氮環境下反應24小時,得聚醯胺酸酯(PAE-1)之濃度12質量%之溶液。 A-5 2.96 g (11.40 mmol), a diamine component B-1 0.52 g (4.80 mmol), B-7 1.07 g (4.80 mmol), B-4 0.41 g (1.20 mmol), NMP 36.5 g, three 0.60 g (5.90 mmol) of ethylamine was placed in a 100 ml four-necked flask equipped with a nitrogen introduction tube and a stir bar, and cooled to about 10 ° C, then 9.96 g (36.00 mmol) of DMT-MM was added, and the reaction was carried out in a nitrogen atmosphere after returning to room temperature. At 24 hours, a solution of a polyamine phthalate (PAE-1) concentration of 12% by mass was obtained.

將NMP 41.4g加入該聚醯胺酸酯(PAE-1)溶液內,冷卻至約10℃後緩緩注入攪拌中之甲醇500mL內析出固體。回收沈澱之固體後,以甲醇200mL分散洗淨2次,100℃下減壓乾燥,得白色粉末狀之聚醯胺酸酯(PAE-1)。該聚醯胺酸酯之數平均分子量為13,500,重量平均分子量為29,000。 41.4 g of NMP was added to the polyacetate (PAE-1) solution, and after cooling to about 10 ° C, a solid was precipitated by slowly injecting 500 mL of methanol in a stirred state. After the precipitated solid was recovered, it was washed twice with 200 mL of methanol, and dried under reduced pressure at 100 ° C to obtain a white powdery polyamine (PAE-1). The polyphthalate had a number average molecular weight of 13,500 and a weight average molecular weight of 29,000.

測取聚醯胺酸酯(PAE-1)2.00g,加入GBL 18.0g後50℃下攪拌24小時使其溶解,確認完全溶解後,加入GBL 3.33g、BCS 10.0g,室溫下攪拌30分鐘,得PAE-1為6.0質量%、GBL為64質量 %、BCS為30質量%之配向劑[AL-12]。 2.00 g of polyperurethane (PAE-1) was measured, and after adding 18.0 g of GBL, it was stirred at 50 ° C for 24 hours to be dissolved. After confirming complete dissolution, GBL 3.33 g, BCS 10.0 g was added, and the mixture was stirred at room temperature for 30 minutes. , PAE-1 is 6.0% by mass, GBL is 64% % and BCS are 30% by mass of an alignment agent [AL-12].

實施例15 Example 15

合成聚醯胺[PA-1:A-6、A-7(50)/B-7]與調製配向劑[AL-13] Synthesis of polyamidamine [PA-1: A-6, A-7 (50) / B-7] and preparation of alignment agent [AL-13]

將B-7 2.23g(10.00mmol)、NMP 16.7g、吡啶1.98g(25.00mmol)加入備有氮導入管與攪拌子之100ml四口燒瓶內,冷卻至約10℃後加入A-6 0.91g(4.80mmol)、A-7 1.02g(5.00mmol),返回室溫後氮環境下反應24小時,得聚醯胺(PA-1)之濃度20質量%之溶液。 2.27 g (10.00 mmol) of B-7, 16.7 g of NMP, and 1.98 g (25.00 mmol) of pyridine were placed in a 100 ml four-neck flask equipped with a nitrogen introduction tube and a stir bar, and cooled to about 10 ° C, and then added to A-6 0.91 g. (4.80 mmol) and A-7 1.02 g (5.00 mmol) were returned to room temperature and reacted for 24 hours in a nitrogen atmosphere to obtain a solution of a concentration of polyamine (PA-1) of 20% by mass.

將NMP 32.2g以8.0%之量加入該聚醯胺(PA-1)溶液內,冷卻至約10℃後緩緩注入攪拌中之甲醇500ml內,析出固體。回收沈澱之固體後,以甲醇200mL分散洗淨2次,100℃下減壓乾燥,得淡褐色粉末狀之聚醯胺(PA-1)。該聚醯胺酸酯之數平均分子量為11,600,重量平均分子量為23,000。 32.2 g of NMP was added to the polyamine (PA-1) solution in an amount of 8.0%, and the mixture was cooled to about 10 ° C, and then slowly poured into 500 ml of methanol under stirring to precipitate a solid. After the precipitated solid was recovered, it was washed twice with 200 mL of methanol, and dried under reduced pressure at 100 ° C to give a pale brown powdery polyamine (PA-1). The polyglycolate had a number average molecular weight of 11,600 and a weight average molecular weight of 23,000.

測取聚醯胺(PA-1)2.00g,加入NMP18.0g後50℃下攪拌24小時使其溶解,確認完全溶解後,加入NMP 3.33g、BCS 10.0g,室溫下攪拌30分鐘,得PA-1為6.0質量%、NMP為64質量%、BCS為30質量%之配向劑[AL-13]。 2.00 g of polyamine (PA-1) was measured, and after adding N8.0 (18.0 g), it was stirred at 50 ° C for 24 hours to dissolve it. After confirming complete dissolution, NMP 3.33 g and BCS 10.0 g were added, and the mixture was stirred at room temperature for 30 minutes. PA-1 was 6.0% by mass, NMP was 64% by mass, and BCS was 30% by mass of the alignment agent [AL-13].

比較例1 Comparative example 1

聚合聚醯胺酸[PAA-5:A-1/B-1]與調製配向劑[AL-14] Polymeric Polyamine Acid [PAA-5: A-1/B-1] and Modulation Orientation Agent [AL-14]

以備有氮導入管與機械攪拌器之50ml四口燒瓶測取B-1 2.16g(20.00mmol),加入NMP 32.9g溶解後,氮環境下冷卻至約10℃,再少許分次加入A-1 3.64g(18.60mmol),返回室溫下反應6小時,得15質量%之聚醯胺酸溶液[PAA-5]。 B-1 2.16g (20.00mmol) was prepared in a 50ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. After dissolving N2.9 32.9g, it was cooled to about 10 ° C in a nitrogen atmosphere, and then added to A- in small portions. 1 3.64 g (18.60 mmol), and returned to room temperature for 6 hours to obtain a 15 mass% polyamine solution [PAA-5].

所得之PAA-5之數平均分子量為9,700,重量平均分子量為19,300。 The obtained PAA-5 had an average number average molecular weight of 9,700 and a weight average molecular weight of 19,300.

以備有攪拌子之50ml三角燒瓶秤取該聚醯胺酸溶液10.0g,加入NMP 7.5g、BCS 7.5g後,室溫下攪拌30分鐘,得PAA-5為6.0質量%、NMP為64質量%、BCS為30質量%之配向劑[AL-14],但冷藏保存時確認會析出聚合物。 10.0 g of the polyaminic acid solution was weighed in a 50 ml Erlenmeyer flask equipped with a stirrer, and 7.5 g of NMP and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 30 minutes to obtain a PAA-5 of 6.0% by mass and an NMP of 64 mass. % and BCS were 30% by mass of the alignment agent [AL-14], but it was confirmed that the polymer was precipitated during storage in a refrigerated state.

比較例2 Comparative example 2

合成可溶性聚醯亞胺[SPI-8:A-1/B-1]與調製配向劑[AL] Synthesis of soluble polyimine [SPI-8:A-1/B-1] and preparation of alignment agent [AL]

以備有攪拌子之100ml三角燒瓶測取比較例1所得之聚醯胺酸溶液[PAA-5]30.0g,加入NMP 45.10g、乙酸酐4.65g、吡啶2.00g後,室溫下攪拌30分鐘,再於50℃下攪拌反應3小時,但反應途中會發生凝膠化,無法調製聚醯亞胺(SPI-8)。故無法調製配向劑AL-15。 30.0 g of the polyaminic acid solution [PAA-5] obtained in Comparative Example 1 was measured in a 100 ml Erlenmeyer flask equipped with a stirrer, and 45.10 g of NMP, 4.65 g of acetic anhydride, and 2.00 g of pyridine were added, followed by stirring at room temperature for 30 minutes. The reaction was further stirred at 50 ° C for 3 hours, but gelation occurred during the reaction, and polyimine (SPI-8) could not be prepared. Therefore, the alignment agent AL-15 cannot be prepared.

比較例3 Comparative example 3

聚合聚醯胺酸[PAA-6:A-1/B-3]與調製配向劑[AL-16] Polymeric polyaminic acid [PAA-6: A-1/B-3] and preparation of alignment agent [AL-16]

以備有氮導入管與機械攪拌器之50ml四口燒瓶測取B-3 2.16(20.00mmol),加入NMP 32.9g溶解後,氮環境下冷卻至約10℃,再少許分次加入A-1 3.77g(19.20mmol),返回室溫下反應6小時,得15質量%之聚醯胺酸溶液[PAA-6]。 B-3 2.16 (20.00 mmol) was taken in a 50 ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. After dissolving N2.9 32.9 g, it was cooled to about 10 ° C in a nitrogen atmosphere, and then added to A-1 in small portions. 3.77 g (19.20 mmol) was returned to room temperature for 6 hours to obtain a 15% by mass polyamine acid solution [PAA-6].

所得之PAA-6之數平均分子量為11,700,重量平均分子量為23,200。 The obtained PAA-6 had an average number average molecular weight of 11,700 and a weight average molecular weight of 23,200.

以備有攪拌子之50ml三角燒瓶秤取該聚醯胺酸溶液10.0g,加入NMP 7.5g、BCS 7.5g後,室溫下攪拌30分鐘,得PAA-6為6.0質量%、NMP為64質量%、BCS為30質量%之配向劑[AL-16]。 10.0 g of the polyaminic acid solution was weighed in a 50 ml Erlenmeyer flask equipped with a stirrer, and 7.5 g of NMP and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 30 minutes to obtain a PAA-6 of 6.0% by mass and an NMP of 64 mass. % and BCS are 30% by mass of an alignment agent [AL-16].

比較例4 Comparative example 4

合成可溶性聚醯亞胺[SPI-9:A-1/B-3]與調製配向劑[AL-17] Synthesis of soluble polyimine [SPI-9: A-1/B-3] and preparation of alignment agent [AL-17]

以備有攪拌子之100ml三角燒瓶測取比較例3所得之聚醯胺酸溶液[PAA-6]30.0g,加入NMP 45.0g、乙酸酐4.65g、吡啶2.00g後,室溫下攪拌30分鐘,再於50℃下攪拌反應3小時,但反應途中會發生凝膠化,無法調製聚醯亞胺(SPI-9)。故無法調製配向劑 AL-17。 30.0 g of the polyaminic acid solution [PAA-6] obtained in Comparative Example 3 was measured in a 100 ml Erlenmeyer flask equipped with a stirrer, and 45.0 g of NMP, 4.65 g of acetic anhydride, and 2.00 g of pyridine were added, followed by stirring at room temperature for 30 minutes. The reaction was further stirred at 50 ° C for 3 hours, but gelation occurred during the reaction, and polyimine (SPI-9) could not be prepared. Therefore, it is impossible to prepare an alignment agent AL-17.

比較例5 Comparative Example 5

聚合聚醯胺酸[PAA-7:A-1/B-5、B-4(10)]與調製配向劑[AL-18] Polymeric polyaminic acid [PAA-7: A-1/B-5, B-4 (10)] and modulation alignment agent [AL-18]

以備有氮導入管與機械攪拌器之50ml四口燒瓶測取B-5 3.570g(18.00mmol)、B-4 0.75g(2.00mmol),加入NMP 31.9g溶解後,氮環境下冷卻至約10℃,再少許分次加入A-1 3.72g(19.0mmol),室溫下反應16小時,得20質量%之聚醯胺酸溶液[PAA-7]。 B-5 3.570g (18.00mmol) and B-4 0.75g (2.00mmol) were measured in a 50ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. After adding NMP 31.9g, it was dissolved in a nitrogen atmosphere. At 10 ° C, A-1 3.72 g (19.0 mmol) was added in portions, and the mixture was reacted at room temperature for 16 hours to obtain a 20% by mass polyamine solution [PAA-7].

所得之PAA-7之數平均分子量為11,800,重量平均分子量為30,000。 The obtained PAA-7 had an average number average molecular weight of 11,800 and a weight average molecular weight of 30,000.

以備有攪拌子之50ml三角燒瓶秤取該聚醯胺酸溶液10.0g,加入NMP 7.5g、BCS 7.5g後,室溫下攪拌30分鐘,得PAA-7為6.0質量%、NMP為64質量%、BCS為30質量%之配向劑[AL-18]。 10.0 g of the polyaminic acid solution was weighed in a 50 ml Erlenmeyer flask equipped with a stirrer, and 7.5 g of NMP and 7.5 g of BCS were added, and the mixture was stirred at room temperature for 30 minutes to obtain a PAA-7 of 6.0% by mass and an NMP of 64 mass. % and BCS are 30% by mass of an alignment agent [AL-18].

比較例6 Comparative Example 6

合成可溶性聚醯亞胺[SPI-10:A-1/B-5、B-4(10),與調製配向劑[AL-19] Synthesis of soluble polyimine [SPI-10: A-1/B-5, B-4 (10), with modulation alignment agent [AL-19]

以備有攪拌子之100ml三角燒瓶測取比較例5所得之聚醯胺酸溶液[PAA-7]30.0g,加入NMP 55.7g、乙酸酐4.62g(45.3mmol)、吡啶1.91g(24.2mmol)後, 室溫下攪拌30分鐘,再於45℃下進行反應,但會發生凝膠化。故無法得到配向劑AL-19。 30.0 g of the polylysine solution [PAA-7] obtained in Comparative Example 5 was measured in a 100 ml Erlenmeyer flask equipped with a stirrer, and 55.7 g of NMP, 4.62 g (45.3 mmol) of acetic anhydride, and 1.91 g (24.2 mmol) of pyridine were added. Rear, After stirring at room temperature for 30 minutes, the reaction was carried out at 45 ° C, but gelation occurred. Therefore, the alignment agent AL-19 could not be obtained.

比較例7 Comparative Example 7

合成可溶性聚醯亞胺[SPI-11:A-1、A-4(50)/B-1、B-6(20)]與調製配向劑[AL-20] Synthesis of soluble polyimine [SPI-11: A-1, A-4 (50) / B-1, B-6 (20)] and preparation of alignment agent [AL-20]

以備有氮導入管與機械攪拌器之50ml四口燒瓶測取B-1 1.08g(10.00mmol)、B-6 1.14g(5.00mmol),加入NMP 25.0g溶解後,氮環境下冷卻至約10℃,再少許分次加入A-4 1.68g(7.50mmol),返回室溫下反應30分鐘後,加入A-1 1.44g(7.35mmol),室溫下反應16小時,得聚醯胺酸溶液。 B-1 1.08g (10.00mmol) and B-6 1.14g (5.00mmol) were measured in a 50ml four-necked flask equipped with a nitrogen inlet tube and a mechanical stirrer. After dissolving by adding NMP 25.0g, it was cooled to about nitrogen atmosphere. At 10 ° C, A-4 1.68 g (7.50 mmol) was added in portions, and the reaction was returned to room temperature for 30 minutes. Then, A-1 1.44 g (7.35 mmol) was added and the mixture was reacted at room temperature for 16 hours to obtain polylysine. Solution.

所得之聚醯胺酸之數平均分子量為13,800,重量平均分子量為39,800。 The obtained polyamic acid had a number average molecular weight of 13,800 and a weight average molecular weight of 39,800.

以備有攪拌子之100ml三角燒瓶測取前述所得之聚醯胺酸溶液30.0g,加入NMP 55.7g、乙酸酐6.71g(65.74mmol)、吡啶5.20g(65.74mmol)後,室溫下攪拌30分鐘,再於90℃下攪拌反應3小時。結束反應後,緩緩注入200ml之甲醇內析出聚合物,攪拌30分鐘後過濾回收固體。以甲醇充分洗淨所得之固體後,100℃下真空乾燥得聚醯亞胺[SPI-11]。該聚醯亞胺之數平均分子量為13,200,重量平均分子量為30,710,醯亞胺化率為62%。 30.0 g of the polyamic acid solution obtained above was measured in a 100 ml Erlenmeyer flask equipped with a stirrer, and 55.7 g of NMP, 6.71 g (65.74 mmol) of acetic anhydride, and 5.20 g (65.74 mmol) of pyridine were added, followed by stirring at room temperature. After a minute, the reaction was further stirred at 90 ° C for 3 hours. After completion of the reaction, the polymer was gradually poured into 200 ml of methanol, and the mixture was stirred for 30 minutes, and then the solid was collected by filtration. The obtained solid was sufficiently washed with methanol, and dried under vacuum at 100 ° C to obtain a polyimine [SPI-11]. The polyimine had a number average molecular weight of 13,200, a weight average molecular weight of 30,710, and a ruthenium iodide ratio of 62%.

以備有攪拌子之50ml三角燒瓶測取SPI- 11 2.00g,加入NMP 18.0g後50℃下攪拌24小時使其溶解,確認完全溶解後,加入NMP 3.33g、BCS 10.0g,室溫下攪拌30分鐘,得SPI-11為6.0質量%、NMP為64質量%、BCS為30質量%之配向劑[AL-20]。 SPI- was taken in a 50 ml Erlenmeyer flask with stirrer 11 2.00g, after adding 18.0g of NMP, it was stirred at 50 ° C for 24 hours to dissolve. After confirming complete dissolution, NMP 3.33g and BCS 10.0g were added, and stirred at room temperature for 30 minutes to obtain SPI-11 of 6.0% by mass, NMP. The alignment agent [AL-20] was 64% by mass and BCS was 30% by mass.

比較例8 Comparative Example 8

合成聚醯胺酸酯[PAE-2:A-5/B-1、B-4(10)]與調製配向劑[AL-21] Synthetic polyphthalate [PAE-2: A-5/B-1, B-4 (10)] and modulation alignment agent [AL-21]

將A-5 2.96g(11.40mmol)、二胺成分之B-1 1.16g(10.80mmol)、B-4 0.45g(1.20mmol)、NMP 30.6g、三乙基胺0.60g(5.90mmol)加入備有氮導入管與攪拌子之100mL四口燒瓶內,冷卻至約10℃後加入DMI-MM 9.96g(36.00mmol),返回室溫後氮環境下反應24小時,得聚醯胺酸酯(PAE-2)之濃度12質量%之溶液。 2.96g (11.40mmol) of A-5, 1.16g (10.80mmol) of B-1 of diamine component, 0.45g (1.20mmol) of B-4, 30.6g of NMP, 0.60g (5.90mmol) of triethylamine A 100 mL four-necked flask equipped with a nitrogen introduction tube and a stirrer was placed, and after cooling to about 10 ° C, 9.96 g (36.00 mmol) of DMI-MM was added, and the mixture was returned to room temperature and reacted for 24 hours in a nitrogen atmosphere to obtain a polyamidate ( A solution having a concentration of 12% by mass of PAE-2).

將NMP 41.4g加入該聚醯胺酸酯(PAE-2)溶液內,冷卻至約10℃後緩緩注入攪拌中之甲醇500mL內析出固體。回收沈澱之固體後,以甲醇200mL分散洗淨2次,100℃下減壓乾燥,得白色粉末狀之聚醯胺酸酯(PAE-2)。該聚醯胺酸酯之數平均分子量為11,700,重量平均分子量為26,000。 41.4 g of NMP was added to the polyperurethane (PAE-2) solution, and after cooling to about 10 ° C, a solid was precipitated by slowly injecting 500 mL of methanol in a stirred state. After the precipitated solid was recovered, it was washed twice with 200 mL of methanol, and dried under reduced pressure at 100 ° C to obtain a white powdery polyamine (PAE-2). The polyphthalate had a number average molecular weight of 11,700 and a weight average molecular weight of 26,000.

測取聚醯胺酸酯(PAE-2)2.00g,加入GBL 18.0g後50℃下攪拌24小時使其溶解,確認完 全溶解後,加入GBL 3.33g、BCS 10.0g,室溫下攪拌30分鐘,得PAE-2為6.0質量%、GBL為64質量%、BCS為30質量%之配向劑[AL-21]。 2.00 g of polyacetate (PAE-2) was measured, and after adding 18.0 g of GBL, it was stirred at 50 ° C for 24 hours to dissolve it. After the total dissolution, GBL 3.33 g and BCS 10.0 g were added, and the mixture was stirred at room temperature for 30 minutes to obtain an alignment agent [AL-21] having a PAE-2 of 6.0% by mass, a GBL of 64% by mass, and a BCS of 30% by mass.

比較例9 Comparative Example 9

合成聚醯胺[PA-2:A-6、A-7(50)/A-1]與調製配向劑[AL-22] Synthesis of polyamidamine [PA-2: A-6, A-7 (50) / A-1] and modulation alignment agent [AL-22]

將B-1 1.08g(10.00mmol)、NMP 16.7g、吡啶1.98g(25.00mmol)加入備有氮導入管與攪拌子之100mL四口燒瓶內,冷卻至約10℃後加入A-6 0.91g(4.80mmol)、A-7 1.02g(5.00mmol),返回室溫後氮環境下反應24小時,但因反應中析出聚合物,故無法得到配向劑AL-22。 B-1 1.08 g (10.00 mmol), NMP 16.7 g, and pyridine 1.98 g (25.00 mmol) were placed in a 100 mL four-neck flask equipped with a nitrogen introduction tube and a stir bar, and cooled to about 10 ° C, and then added to A-6 0.91 g. (4.80 mmol) and A-7 1.02 g (5.00 mmol) were reacted for 24 hours in a nitrogen atmosphere after returning to room temperature. However, since the polymer was precipitated during the reaction, the alignment agent AL-22 could not be obtained.

比較例10 Comparative Example 10

合成聚醯胺[PA-3:A-6、A-7(50)/B-3]與調製配向劑[AL-23] Synthesis of polyamines [PA-3: A-6, A-7 (50) / B-3] and preparation of alignment agent [AL-23]

將B-3 1.08g(10.00mmol)、NMP 16.7g、吡啶1.98g(25.00mmol)加入備有氮導入管與攪拌子之100mL四口燒瓶內,冷卻至約10℃後加入A-6 0.91g(4.80mmol)、A-7 1.02g(5.00mmol),返回室溫後氮環境下反應24小時,但反應中會析出聚合物,故無法得到配向劑AL-23。 B-3 1.08 g (10.00 mmol), NMP 16.7 g, and pyridine 1.98 g (25.00 mmol) were placed in a 100 mL four-neck flask equipped with a nitrogen introduction tube and a stir bar, and cooled to about 10 ° C, and then added to A-6 0.91 g. (4.80 mmol) and A-7 1.02 g (5.00 mmol) were reacted for 24 hours in a nitrogen atmosphere after returning to room temperature. However, the polymer was precipitated during the reaction, and thus the alignment agent AL-23 could not be obtained.

比較例11 Comparative Example 11

合成聚醯胺[PA-4:A-6/B-3]與調製配向劑[AL-24] Synthesis of polyamidamine [PA-4: A-6/B-3] and preparation of alignment agent [AL-24]

將B-3 1.08g(10.0mmol)、NMP 16.7g、吡啶1.98g(25.00mmol)加入備有氮導入管與攪拌子之100mL四口燒瓶內,冷卻至約10℃後加入A-6 1.50g(9.70mmol),返回室溫後氮環境下反應24小時。結束反應後,緩緩注入300ml之丙酮內析出固體。回收沈澱之固體後,以甲醇200mL分散洗淨2次,100℃下減壓乾燥,得淡灰色粉末狀之聚醯胺(PA-4)。該聚醯胺之數平均分子量為8,500,重量平均分子量為17,900。 B-3 1.08 g (10.0 mmol), NMP 16.7 g, and pyridine 1.98 g (25.00 mmol) were placed in a 100 mL four-neck flask equipped with a nitrogen introduction tube and a stir bar, and cooled to about 10 ° C, then A-6 1.50 g was added. (9.70 mmol), after returning to room temperature, the reaction was carried out for 24 hours under a nitrogen atmosphere. After the completion of the reaction, a solid was precipitated by slowly injecting 300 ml of acetone. After the precipitated solid was recovered, it was washed twice with 200 mL of methanol, and dried under reduced pressure at 100 ° C to obtain a light gray powdery polyamine (PA-4). The polyamine had a number average molecular weight of 8,500 and a weight average molecular weight of 17,900.

測取聚醯胺(PA-4)2.00g,加入NMP 18.0g後50℃下攪拌24小時使其溶解,確認完全溶解後,加入NMP 3.33g、BCS 10.0g,室溫下攪拌30分鐘,得PA-4為6.0質量%、NMP為64質量%、BCS為30質量%之配向劑[AL-24]。 2.00 g of polyamine (PA-4) was measured, and 18.0 g of NMP was added thereto, and the mixture was stirred at 50 ° C for 24 hours to be dissolved. After confirming complete dissolution, 3.33 g of NMP and 10.0 g of BCS were added, and the mixture was stirred at room temperature for 30 minutes. The PA-4 was 6.0% by mass, the NMP was 64% by mass, and the BCS was 30% by mass of the alignment agent [AL-24].

使用本發明二胺之聚合物相對於溶劑具 有較高溶解性,因此既使無法成為比較例1、2、4、6、10、11般之可溶性聚合物之物,導入本發明之單體仍可形成可溶性聚合物。即,因可提高相對於溶劑之溶解性,故可導入大量具有良好之基板潤濕性的弱溶劑,又印刷時不易發生析出或白化等,故可提升塗佈、成膜性,得良好印刷性之液晶配向劑。 Polymer using the diamine of the present invention relative to a solvent Since it has high solubility, even if it is not a soluble polymer like Comparative Example 1, 2, 4, 6, 10, 11, the soluble polymer can be formed by introducing the monomer of the present invention. In other words, since the solubility with respect to the solvent can be improved, a large amount of a weak solvent having a good substrate wettability can be introduced, and precipitation or whitening is less likely to occur during printing, so that coating and film forming properties can be improved, and good printing can be obtained. Liquid crystal alignment agent.

產業上利用可能性 Industrial use possibility

藉由本發明之液晶配向處理劑可得,加強摩擦時之膜剝離或削減、提高電壓保持率,且既使施加直流電壓也難使初期之電荷蓄積的液晶配向膜。因此使用本發明之液晶配向處理劑所製作之液晶顯示元件可為,高信賴性之液晶顯示裝置,適用於TN液晶顯示元件、STN液晶顯示元件、TFT液晶顯示元件、VA液晶顯示元件、IPS液晶顯示元件、OCB液晶顯示元件等使用各種方式之顯示元件。 According to the liquid crystal alignment treatment agent of the present invention, it is possible to obtain a liquid crystal alignment film in which the film is peeled off or reduced during rubbing, the voltage holding ratio is increased, and the initial charge is hard to be applied even when a DC voltage is applied. Therefore, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention can be a highly reliable liquid crystal display device, and is suitable for a TN liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, a VA liquid crystal display element, an IPS liquid crystal. Display elements using various modes such as display elements, OCB liquid crystal display elements, and the like.

Claims (11)

一種聚合物,其為由使用下述一般式[1]所表示之二胺所得的聚醯胺、聚醯胺酸、聚醯胺酸酯,或該聚醯胺酸及/或聚醯胺酸酯脫水閉環(醯亞胺化)所得之聚醯亞胺所形成。 (式中,A表示可藉由熱而脫離所得之有機基;NHA基為具備n個(n=1或2),且相對於胺基(NH2基)存在於鄰位;又,胺基相互間存在於間位或對位)。 A polymer obtained by using a polyamine represented by the following general formula [1], polylysine, polylysine, or polylysine and/or polylysine It is formed by the polyimine obtained by the ester dehydration ring closure (oxime imidization). (wherein A represents an organic group which can be removed by heat; the NHA group has n (n = 1 or 2) and is present in the ortho position relative to the amine group (NH 2 group); They exist in the meta or para position. 如申請專利範圍第1項之聚合物,其中一般式[1]中,A之可藉由熱而脫離所得之有機基為tert-丁氧基羰基。 The polymer of claim 1, wherein in the general formula [1], the organic group which can be removed by heat is a tert-butoxycarbonyl group. 如申請專利範圍第1項之聚合物,其中含有5至95mol%之一般式[1]所表示之二胺。 A polymer according to claim 1 which contains 5 to 95 mol% of the diamine represented by the general formula [1]. 如申請專利範圍第2項之聚合物,其中含有5至95mol%之一般式[1]所表示之二胺 The polymer of claim 2, which contains 5 to 95 mol% of the diamine represented by the general formula [1] 如申請專利範圍第1項之聚合物,其中含有5至50mol%之含有下述一般式[2]所表示之支鏈的二胺, (式中,R1表示單鍵、二價之有機基;X1、X2、X3各自獨立表示苯環或環己烷環;p、q、r各自獨立表示0或1之整數;R2表示氫原子、碳數1至22之烷基或具有巢類骨架之碳數12至25的二價之有機基)。 The polymer of claim 1 which contains 5 to 50 mol% of a diamine having a branched chain represented by the following general formula [2], Wherein R 1 represents a single bond or a divalent organic group; and X 1 , X 2 and X 3 each independently represent a benzene ring or a cyclohexane ring; and p, q and r each independently represent an integer of 0 or 1; 2 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or a divalent organic group having 12 to 25 carbon atoms of a nest skeleton. 如申請專利範圍第2項之聚合物,其中含有5至50mol%之含有下述一般式[2]所表示之支鏈的二胺, (式中,R1表示單鍵、二價之有機基;X1、X2、X3各自獨立表示苯環或環己烷環;p、q、r各自獨立表示0或1之整數;R2表示氫原子、碳數1至22之烷基或具有巢類骨架之碳數12至25的二價之有機基)。 The polymer of claim 2, which contains 5 to 50 mol% of a diamine having a branched chain represented by the following general formula [2], Wherein R 1 represents a single bond or a divalent organic group; and X 1 , X 2 and X 3 each independently represent a benzene ring or a cyclohexane ring; and p, q and r each independently represent an integer of 0 or 1; 2 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or a divalent organic group having 12 to 25 carbon atoms of a nest skeleton. 如申請專利範圍第3項之聚合物,其中含有5至50mol%之含有下述一般式[2]所表示之支鏈的二胺, (式中,R1表示單鍵、二價之有機基;X1、X2、X3各自獨立表示苯環或環己烷環;p、q、r各自獨立表示0或1之整數;R2表示氫原子、碳數1至22之烷基或具有巢類骨架之碳數12至25的二價之有機基)。 The polymer of claim 3, which contains 5 to 50 mol% of a diamine having a branched chain represented by the following general formula [2], Wherein R 1 represents a single bond or a divalent organic group; and X 1 , X 2 and X 3 each independently represent a benzene ring or a cyclohexane ring; and p, q and r each independently represent an integer of 0 or 1; 2 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or a divalent organic group having 12 to 25 carbon atoms of a nest skeleton. 一種液晶配向劑,其特徵為,含有如申請專利範圍第1至7項中任何一項之聚合物。 A liquid crystal alignment agent comprising the polymer according to any one of claims 1 to 7. 一種液晶配向膜,其為使用如申請專利範圍第8項之液晶配向劑。 A liquid crystal alignment film which is a liquid crystal alignment agent as used in claim 8 of the patent application. 一種液晶顯示元件,其為具備如申請專利範圍第9項之液晶配向膜。 A liquid crystal display element comprising a liquid crystal alignment film according to item 9 of the patent application. 一種二胺,其為下述一般式[1-5]或[1-6]所表示, A diamine which is represented by the following general formula [1-5] or [1-6],
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