CN100501532C - Liquid crystal directing agent, liquid crystal oriented film and liquid crystal display element - Google Patents

Liquid crystal directing agent, liquid crystal oriented film and liquid crystal display element Download PDF

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CN100501532C
CN100501532C CN 200510051339 CN200510051339A CN100501532C CN 100501532 C CN100501532 C CN 100501532C CN 200510051339 CN200510051339 CN 200510051339 CN 200510051339 A CN200510051339 A CN 200510051339A CN 100501532 C CN100501532 C CN 100501532C
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crystal
element
directing
display
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CN1664657A (en )
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清水成夫
西川通则
林英治
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Jsr株式会社
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Abstract

本发明提供一种液晶定向剂,该液晶定向剂能够形成防止显示不佳,经长时间驱动后残像特性仍然良好、不会降低使液晶定向的能力、且对于光和热的电压残留率下降少的液晶定向膜。 The present invention provides a liquid crystal aligning agent, which prevents liquid crystal aligning agent capable of forming a poor display, afterimage characteristics after long-time driving is still good, the liquid crystal orientation without reducing the ability for voltage and the residual rate decreased to less light and heat the liquid crystal alignment film. 本发明通过一种液晶定向剂组合物实现,该组合物包括四烷氧基硅烷之类的4官能团硅化合物、三烷氧基硅烷之类的3官能团化合物以及每摩尔烷氧基之类的官能基团与0.8~3.0摩尔水反应的产物和乙二醇醚类溶剂。 The present invention is achieved by a liquid crystal aligning agent composition is realized, the composition includes 4 functional silicon compound a tetraalkoxysilane or the like, a trifunctional compound functional trialkoxysilane per mole of such alkoxy and the like the product glycol ether solvent and water of reaction groups with a 0.8 molar to 3.0.

Description

液晶定向剂、液晶定向膜以及液晶显示元件 The liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display element

技术领域 FIELD

本发明涉及液晶定向剂、液晶定向膜和液晶显示元件,更具体地,涉及一种液晶定向层、能够形成该液晶定向层的液晶定向剂以及液晶显示元件,其中液晶定向层液晶定向性优良,且在光照和高温的严酷环境下或长时间驱动后也不会损害电压残留率等电特性,在保持良好的液晶定向状态下,也难以产生残像显像。 The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display device, and more particularly, to a liquid crystal alignment layer, the liquid crystal alignment layer capable of forming a liquid crystal alignment agent and a liquid crystal display element, wherein the liquid crystal alignment layer having excellent crystal orientation, and at a high temperature and harsh environment light or after prolonged electric characteristics are not impaired driving voltage remaining rate, while maintaining a good liquid crystal alignment state, it is difficult to produce a residual image developing.

背景技术 Background technique

目前,已知的液晶显示元件有具有TN型(扭转向列)液晶细胞的TN型液晶显示元件,该元件在设有透明导电膜的基板表面上形成聚酰胺酸、聚酰亚胺等液晶定向膜作为液晶显示元件的基板,将两块基板相对设置,在其间隙内形成具有正介电各向异性的向列型液晶层,形成夹层结构的细胞,液晶分子的长轴从一块基板向另一块基板连续地扭转90度。 Currently, there are known liquid crystal display device having a TN (twisted nematic) liquid crystal cell of TN type liquid crystal display element which is provided in the polyamic acid is formed on the surface of the transparent conductive film substrate, such as polyimide liquid crystal orientation film as a liquid crystal display element substrate, the two substrates disposed opposite, forming a positive dielectric anisotropy nematic liquid crystal layer to form a cell sandwich structure, the long axis of the liquid crystal molecules from one substrate to another within the gap a substrate is continuously twisted 90 degrees. 此外,正在开发能够实现比TN型液晶显示元件对比度更高的STN(超扭转向列)型液晶显示元件和视角依赖性少的IPS(面内扭转(In-Plane Switching))型液晶显示元件、VA(Vertical Allignment)型液晶显示元件。 Also being developed to achieve higher than the TN type liquid crystal display device contrast STN (super twisted nematic) type liquid crystal display element and less viewing angle dependence IPS (in-plane torsion (In-Plane Switching)) type liquid crystal display element, VA (Vertical allignment) type liquid crystal display element.

这样的各种液晶显示元件的工作原理分为透射型和反射型。 Such various liquid crystal display device is divided into working principle of a transmission type and a reflection type.

透射型液晶显示元件在元件驱动时,利用元件背面的背面光用光源的透射光强度的变化进行显示。 Transmissive liquid crystal display element when the driving element, a display light source changes in transmitted light intensity by the rear surface of the back member. 反射型液晶显示元件不使用背面光用光源,在元件驱动时,利用太阳光等外来光的反射强度的变化进行显示,由于其与透射型相比电力消耗较少,因此认为对于室外使用是特别有利的。 Reflection type liquid crystal display device using the back light source does not, at the time of the drive element, use changes in the reflection intensity of the external light such as sunlight display, since less power consumption as compared with transmissive type, it is considered particularly for outdoor use advantageous.

在透射型液晶显示元件中,液晶定向膜总是用来自背面光源的光照射。 In the transmission type liquid crystal display element, the liquid crystal alignment film is irradiated with light from the back is always source. 特别是在商业和近年来的家庭影院中需求较高的液晶投影仪的应用中,采用金属卤化物灯等照射强度非常大的光源。 In recent years, particularly in commercial and home theater applications in high demand in the liquid crystal projector, using a metal halide lamp, irradiation intensity of the light source is very large. 反射型液晶显示元件在室外使用的可能性大,在这种情况下用含有强紫外光的太阳光作为光源。 Reflective liquid crystal display element possibility of outdoor use large, in this case with strong sunlight containing ultraviolet light as a light source. 此外,使用反射型时,在原理上,光通过元件内部的距离比透射型长。 Further, when using a reflection type, in principle, the optical element by a distance longer than the internal transmission type.

在液晶显示元件的制造工序中,从缩短制造过程和提高产率的角度出发,首选使用的是液晶滴入方式即ODF(One Drop Fill)方式。 Show a manufacturing process of the liquid crystal element, to shorten the manufacturing process and from the viewpoint of improving the yield viewpoint, the preferred embodiment uses a liquid crystal dropwise i.e., ODF (One Drop Fill) mode. ODF方式与向事先用热固化性密封剂组装的空液晶细胞中注入液晶的现有方法不同,其在涂布了液晶定向膜的单侧基板的必要部位涂布紫外光固化性密封剂后,向必要部位滴入液晶,再贴合另一块基板,然后整体进行紫外光照射使密封剂固化,制成液晶细胞。 ODF manner to the conventional method previously injected with an empty liquid crystal cell assembled heat-curing sealing agent of different, after which the curable sealant coated substrate, one side of the liquid crystal alignment film coated necessary part of the ultraviolet light, was added dropwise to the necessary part liquid, paste together the other substrate, and the whole was irradiated with ultraviolet light cure the sealing agent, the liquid crystal cell is made. 此时照射的紫外光的强度通常为数焦耳/cm2。 At this time, the irradiation intensity of ultraviolet light is typically several Joules / cm2. 即在液晶显示元件的制造工序中,液晶定向膜与液晶同时用这种强紫外光进行照射。 I.e., the manufacturing process of the liquid crystal display device, the liquid crystal and the liquid crystal alignment film is irradiated simultaneously with this strong ultraviolet light.

在使用透射型液晶显示元件时,考虑到伴随着高强度的光照射,驱动时液晶显示元件系统本身的温度有时会升高。 When using a transmission type liquid crystal display device, taking into account along with the irradiation light with high intensity, the temperature of the liquid crystal display element drive system itself increases sometimes. 并且,随着液晶显示元件多用途化,还考虑到在室外等的使用,或者设置在停车场内私家汽车内等比一般室温高的温度下的使用和设置环境。 And, as the purpose of the liquid crystal display device, it is also contemplated for use in the outdoors, and the use of geometric or set environment setting a high temperature in the room is generally private car in the parking lot.

在这种液晶显示元件中,随着其高性能化、多用途化等,需要一种在经受光和热的严酷环境后或者长时间驱动后液晶定向性和电压残留率等电特性、或者残像特性比现有的更加优良的元件。 In the liquid crystal display element, with its high performance, multi-purpose etc., the electrical properties of liquid crystal orientation and residual voltage ratio Once a need for a light and heat after being subjected to the harsh environment or over a long time, or afterimage more excellent than the conventional element characteristics.

作为构成液晶显示元件的液晶定向膜的材料,根据现有技术,已知的有聚酰亚胺、聚酰胺和聚酯等树脂。 Materials liquid crystal alignment film constituting the liquid crystal display element, according to the prior art, there have been known a polyimide, polyamide and polyester resins. 特别是聚酰亚胺,由于在树脂中其在耐热性、与液晶的亲和性、机械强度等方面表现出优良的物理特性,被用于许多液晶显示元件。 In particular polyimide, since it exhibits excellent physical properties in terms of heat resistance, affinity with liquid crystals, mechanical strength, etc. in a resin, are used in many liquid crystal display element.

但是,近年来的液晶显示元件朝着高性能化和多用途化发展,在上述高温环境和光照的严酷环境中设置使用的几率在增加,并且,在制造工序中需要进一步缩短过程和提高产率,另一方面还要求液晶显示元件的寿命更长。 However, in recent years, liquid crystal display element toward the development of multi-purpose and high performance, the high-temperature environment is provided in the harsh environment and the light used in increasing the probability, and, in the manufacturing process and the need to further reduce the process to increase the yield , on the other hand also requires a longer life liquid crystal display element. 与此同时,不容许由于对以往容许的高温环境和光照的耐受性不够而产生表面缺陷或残像。 At the same time, we do not allow high-temperature environment because of insufficient light resistance and allow conventional or surface defects generated afterimage.

因此,以往作为液晶定向膜使用的聚酰胺酸和聚酰亚胺有机树脂对光和热的耐受性还不够。 Thus, polyamic acid and the polyimide resin conventionally used as an organic alignment film on the liquid crystal light and heat resistance is not enough. 因此,需要一种不会降低液晶显示元件在面内使液晶均勾定向的能力、且对光和热耐受性良好的新材料. Therefore, a liquid crystal display device without reducing the ability to make the liquid crystal are oriented in the inner surface of the hook, and a good light and heat resistance of the new material.

在特开平9 - 281502号公报中公开了一种垂直定向膜,其通过使四乙氧基硅烷等含4个烷氧基的硅化合物(A)与十八烷基三乙氧基硅烷等含3个烷氧基的硅化合物(B)在醇溶剂中在草酸催化剂存在下于5(TC~18(TC下进行加热反应,生成(A)和(B)共缩合物聚硅氧烷溶液,以该溶液作为涂布液,将其涂布于电极基板表面上,所得涂膜在80~400°C下进行热固化而制得。该公报进一步说明了所述垂直定向膜垂直定向性、重现性、耐热性和均勾性优良,涂布液的稳定性也优异。 Discloses a vertical orientation film Publication No. 281502, which contains (A) and octadecyl triethoxysilane and tetraethoxysilane by reacting 4-alkoxy-containing silicon compound - 9 KOKAI the silicon compound (B). 3 alkoxy groups in the alcohol solvent in the presence of a catalyst of oxalic acid in 5 (TC ~ 18 the reaction was heated (at TC, generating (a) and (B) co-condensate polysiloxane solution, in this solution as a coating liquid, applying the resultant coating film on the surface of the electrode substrate at 80 ~ 400 ° C heat curing the same. this publication further illustrated vertical orientation to the vertical orientation film, heavy now, heat resistance, and are excellent in hook, stability of the coating liquid is also excellent.

但是,这种垂直定向膜或其形成方法还不完善。 However, such a method of forming a vertical alignment film or not perfect. 对于上述特开平9 - 281502号中记载的垂直定向膜,所得涂膜中恐怕会残留未反应的硅氧烷基团。 For the above-mentioned Japanese Patent Publication 9 - vertical orientation film siloxane groups described in No. 281502, probably resulting coating film may remain unreacted. 未反应的硅氧烷基团不稳定,液晶中所含微量水分或液晶细胞密封剂所带入的水分使得硅氧烷基团水解,生产醇分子,该醇分子扩散至液晶中,导致出现显示不佳等。 Siloxane groups unreacted unstable, the liquid crystal contained in the liquid crystal cell or trace moisture sealant into the water so that the hydrolysis of siloxane groups, the production of alcohol molecules in the alcohol diffused into the liquid crystal, resulting in the display not so good.

发明内容本发明是鉴于上述情况而作出的,本发明的目的是提供一种液晶定向剂,该液晶定向剂通过充分地进行水解反应,使娃氧坑99%或以上被转化,从而能够形成防止这种显示不佳、经长时间驱动后残像特性仍然良好、不会降低使液晶定向的能力、且对于光和热电压残留率下降少的液晶定向膜。 The present invention has been made in view of the above circumstances, the object of the present invention is to provide a liquid crystal aligning agent, the liquid crystal aligning agent by sufficiently hydrolysis reaction, the baby pit 99% or more oxygen is converted, it is possible to prevent the formation of such a display poor afterimage characteristics after long-time driving is still good, the liquid crystal orientation without reducing the ability for voltage and the liquid crystal alignment film residual rate decreased less light and heat.

本发明的另一目的是提供一种应用本发明液晶定向剂的具有如上所述各优良性能的液晶定向膜及其制造方法。 Another object of the present invention is to provide a liquid crystal aligning agent of the present invention is applied to a liquid crystal alignment film manufacturing method thereof each having excellent properties as mentioned above.

本发明的又一个目的是提供具有本发明液晶定向膜的液晶显示元件。 Still another object of the present invention is to provide a liquid crystal alignment film having crystal display device of the present invention.

本发明的其它目的和优点可以通过以下说明而获悉。 Other objects and advantages of the present invention can be learned from the following description.

根据本发明,本发明的上述目的和优点,第一,是通过一种液晶定向剂而达成的,所述液晶定向剂的特征在于包括(I)特定两种硅氧烷和水的反应产物和(II)溶剂,具体地说,包括(I)下述式(I)表示的硅化合物、下述式(2)表示的硅化合物和水的反应产物(以下称为“反应产物(I)”)以及(II)述式(3)表示的溶剂, According to the present invention, the above objects and advantages of the present invention, the first, is directed through a liquid agent reached, characterized in that the liquid crystal aligning agent comprising (I) a reaction product of a particular two siloxane and water, and (II) a solvent, in particular, comprising a silicon compound (I) represented by the following formula (I), the reaction product of a silicon compound and water by the following formula (2) (hereinafter referred to as "reaction product (I)" ) and a solvent (3) (II) of the above formula,

Si(OR1)4..................(I) Si (OR1) 4 .................. (I)

其中R1为氢原子、氟原子或一价的有机基团, Wherein R1 is a hydrogen atom, a fluorine atom or a monovalent organic group,

RSi(OR2)3..................(2) RSi (OR2) 3 .................. (2)

其中R为一价的有机基团,而R2为氢原子、氟原子或一价的有机基团, Wherein R is a monovalent organic group, and R2 is a hydrogen atom, a fluorine atom or a monovalent organic group,

CH3 CH3

I I

R3O (CH) m (CH2) n0H ..........(3) R3O (CH) m (CH2) n0H .......... (3)

其中,R3为甲基、乙基、正丙基、异丙基、正丁基或叔丁基,m为0或者I,而n为I、2或3。 Wherein, R3 is methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl group, m is 0 or I, and n is I, 2 or 3.

根据本发明,本发明的上述目的和优点,第二,是通过液晶定向膜的形成方法而达成的,该方法特征在于包括将本发明的液晶定向膜涂布于基板的工序和加热涂布的基板使涂膜固化的工序》 According to the present invention, the above objects and advantages of the present invention, the second, by a method of forming a liquid crystal alignment film being reached, the method characterized by comprising the liquid crystal alignment film according to the present invention is applied to a step of heating the coated substrate, and of the substrate to cure the coating step "

根据本发明,本发明的上述目的和优点,第三,是通过采用上述本发明方法形成的液晶定向膜而达成的。 According to the present invention, the above objects and advantages of the present invention, the third, is by using a liquid crystal alignment film formed in the method of the present invention and achieved.

根据本发明,本发明的上述目的和优点,最后,是通过具有本发明液晶定向膜的液晶显示元件而达成的。 According to the present invention, the above objects and advantages of the present invention, finally, is achieved by the present invention has a liquid crystal alignment film of the liquid crystal display element.

根据本发明,与现有的材料相比,通过使用应用硅类材料的液晶定向剂,能够制造一'种液晶显不元件,该液晶显TF元件即使经受进行光照射和热处理的严酷环境后,或者长时间驱动后,其优良的液晶定向性、电压残留率和残像特性也不会较大程度地降低。 According to the present invention, compared with the conventional material using the liquid crystal aligning agent by application of silicon-based materials, can be produced a 'kind of liquid crystal display element is not, after which TF liquid crystal display element even when subjected to light irradiation and heat treatment of the harsh environment, or after long-time driving, which is excellent in liquid crystal orientation, the residual voltage ratio characteristic and the afterimage is not reduced to a large extent.

使用本发明液晶定向剂制作的液晶显示元件,除了能够适用于TN型和STN型液晶显示元件以外,根据所选用的液晶,还能够适用于SH(Super Homeotropic)型、IPS(In - Plane Switching)型、VA(Vertical Allignment)型、强介电性和反强介电性液晶显示元件等。 Liquid using the liquid crystal aligning agent of the present invention is fabricated display device, in addition to be applied to TN type and STN type liquid crystal display to the elements, the liquid crystal is chosen, also be applied to SH (Super Homeotropic) type, IPS (In - Plane Switching) type, VA (Vertical allignment) type, ferroelectric and antiferroelectric liquid crystal display element and the like.

并且,具有用本发明液晶定向剂形成的定向膜的液晶显示元件液晶定向性和可靠性优良,能够有效地用于各种装置,例如用于台式计算机、手表、台钟、系数显示屏、文字处理器、个人计算机、液晶数据投影仪、液晶电视机、电子报纸等显示装置。 And the liquid crystal, the orientation film having a liquid crystal aligning agent of the present invention, a liquid crystal display element formed in the orientation and excellent reliability, can be effectively used in various devices, for example, desktop computers, watches, table clocks, coefficient display, text a display device processor, personal computer, liquid crystal data projectors, liquid crystal televisions, electronic newspaper and the like.

具体实施方式液晶定向剂本发明的液晶定向剂包括(I)反应产物(I)和(II)溶剂。 DETAILED DESCRIPTION liquid crystal aligning agent The liquid crystal aligning agent of the present invention comprises (I) a reaction product (I) and (II) a solvent. (I)反应产物(I)为下述式(I)表示的硅化合物(以下称为“硅化合物(I)”)、下述式(2)表示的硅化合物(以下称为“硅化合物(2)”)和水的反应产物 (I) the reaction product (I) is a silicon compound represented by the following formula (I) (hereinafter referred to as "silicon compound (I)"), the following formula (2) is a silicon compound represented by (hereinafter referred to as "silicon compound ( the reaction product of 2) ") and water

Si(OR1)4..................(I) Si (OR1) 4 .................. (I)

其中R1为氢原子、氟原子或一价的有机基团, Wherein R1 is a hydrogen atom, a fluorine atom or a monovalent organic group,

RSi(OR2)3..................(2) RSi (OR2) 3 .................. (2)

其中R为一价的有机基团,而R2为氢原子、氟原子或一价的有机基团。 Wherein R is a monovalent organic group, and R2 is a hydrogen atom, a fluorine atom or a monovalent organic group.

式(I)中,作为R1的一价有机基团,可以列举例如烷基、芳基、烯丙基、酰基、环氧丙基等。 In the formula (the I), R1 is a monovalent organic group, and examples thereof include an alkyl group, an aryl group, an allyl group, an acyl group, an epoxy group and the like. 这里,烷基可以列举例如甲基、乙基、丙基、丁基等。 Here, the alkyl group may include methyl, ethyl, propyl, butyl and the like. 优选碳原子数为I〜5的烷基、这些烷基可以为链状、也可以分支,并且氢原子还可以被氟原子等取代。 I~5 number of carbon atoms is preferably an alkyl group, such group may be linear, it may be branched, and the hydrogen atoms may also be substituted with a fluorine atom. 芳基可以列举例如苯基、萘基、甲苯基、乙苯基、氣代苯基、溴代苯基、氟代苯基等。 Aryl group may include phenyl, naphthyl, tolyl, ethylphenyl, gas substituted phenyl, bromophenyl, fluorophenyl and the like.

酰基可以列举例如乙酰基、苯甲酰基、甲酰基、丙酰基等。 Acyl group may include acetyl, benzoyl, formyl, and propionyl.

化合物(I)的具体实例可以列举四曱氧基硅烷、四乙氧基硅烷、四正丙氧基硅烷、四异丙氧基硅烷、四正丁氧基硅烷、四仲丁氧基硅烷、四叔丁氧基硅烷、四苯氧基硅烷、四乙酰氧基硅烷、四环氧丙氧基硅烷等。 Specific examples of Compound (I) may include four Yue silane, tetraethoxysilane, tetra-n-propoxy silane, tetra i-propoxy silane, tetra-n-butoxy silane, tetra-sec-butoxy silane, tetra tert-butoxy silane, tetraphenoxy silane, tetraacetoxy silane, tetra glycidoxy silane. 它们可以I种或者2种或以上一起使用。 They may be used either alone or I with two or more.

式(2)中,R为一价的有机基团,而R2为氢原子、氟原子或一价的有机基团。 Formula (2), R is a monovalent organic group, and R2 is a hydrogen atom, a fluorine atom or a monovalent organic group. R2的一价有机基团可以列举与R1同样的基团。 R2 is a monovalent organic group include the same groups as R1.

此外,R的一价有机基团优选可以列举例如可选可被氨基、环氧丙氧基或三氟甲基取代的Cl〜4的烷基、乙缔基和苯基;碳原子数为16或以上的直链烷基;可被取代且具有至少一个降冰片烷环的一价有机基团;可被取代且具有至少一个甾体骨架的一价有机基团;具有带有氟原子、三氟甲基或三氟甲氧基取代基芳香环的且碳原子数为8或以上的一价基团;以及具有肉桂酰基或查耳酮基(力儿3 二/U基)的感光性基团等。 Further, R is a monovalent organic group may preferably include, for example, may optionally substituted by amino, glycidoxy or trifluoromethyl-substituted alkyl group of Cl~4, ethyl group and phenyl association; 16 carbon atoms, or more straight chain alkyl; and can be substituted by a monovalent organic group having at least a norbornane ring; and may be substituted by a monovalent organic group having at least one steroid skeleton; with having a fluorine atom, tris and the carbon number of fluorine atoms or trifluoromethoxy substituent is an aromatic ring 8 or more a monovalent group; and a cinnamoyl group or chalcone group (two force children 3 / U-yl) photosensitive group group and so on. R为任选可被氨基、环氧丙氧基或三氟甲基取代的CI〜4烷基、乙烯基和笨基的化合物(以下称为化合物(A))的具体实例可以列举甲基三甲氧基硅烷、甲基三乙氧基硅烷、曱基三正丙氧基硅烷、甲基三异丙氧基硅烷、甲基三正丁氧基硅烷、甲基三仲丁氧基硅烷、甲基叔丁氧基硅烷、甲基三苯氧基硅烷、乙基甲氧基硅烷、乙基三乙氧基硅烷、乙基三正丙氧基硅烷、乙基三异丙氧基硅烷、乙基三正丁氧基硅烷、乙基三仲丁氧基硅烷、乙基三叔丁氧基硅烷、乙基三苯氧基硅烷、乙烯基三曱氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三正丙氧基硅烷、乙烯基三异丙基硅烷、乙烯基三正丁氧基硅烷、乙烯基三仲丁氧基硅烷、乙烯基三叔丁氧基硅烷、乙烯基三笨氧基娃烷、正丙基三甲氧基桂烷、正丙基三乙氧基娃燒、正丙基三正丙氧基娃燒、正丙基三异两氧基娃燒、 Specific examples of R may be optionally substituted by amino, glycidoxy or trifluoromethyl CI~4 alkyl compound, and stupid vinyl group (hereinafter referred to as compound (A)) may include methyltrimethoxysilane silane, methyl triethoxysilane, Yue-n-propoxy silane, methyl triisopropoxysilane, methyl tri-n-butoxy silane, methyl tri-sec-butoxy silane, methyl tert-butoxy silane, methyl triphenoxy silane, ethyl methoxy silane, ethyl triethoxysilane, ethyl tri-n-propoxysilane, ethyl triisopropoxysilane, ethyl three n-butoxy silane, ethyl tri-sec-butoxy silane, ethyl tri-t-butoxy silane, ethyl triphenoxy silane, vinyltris Yue silane, vinyl triethoxy silane, vinyl tri-n-propoxy silane, vinyl triisopropyl silane, vinyl tri-n-butoxy silane, vinyl tri-sec-butoxy silane, vinyl tri-t-butoxy silane, vinyltris stupid baby alkoxy group , n-propyl trimethoxy Katsura alkoxy, n-propyl triethoxy baby burn, n-propyl tri-n-propoxy baby burn, tri-iso-propyl group two baby burn, 丙基三正丁氧基硅烷、正丙基三仲丁氧基硅烷、正丙基叔丁氧基硅烷、 正丙基三苯氧基硅烷、异丙基三甲氧基硅烷、异丙基三乙氧基硅烷、异丙基三正丙氧基硅烷、异丙基三异丙氧基硅烷、异丙基三正丁氧基硅烷、异丙基三仲丁氧基硅烷、异丙基叔丁氧基硅烷、异丙基三苯氧基硅烷、正丁基三甲氧基硅烷、正丁基三乙氧基硅烷、正丁基三正丙氧基硅烷、正丁基三异丙氧基硅烷、正丁基三正丁氧基娃烷、正丁基三仲丁氧基硅烷、正丁基叔丁氧基硅烷、正丁基三苯氧基硅烷、仲丁基三甲氧基硅烷、仲丁基-i-三乙氧基硅烷、仲丁基三正丙氧基硅烷、仲丁基三异丙氧基硅烷、仲丁基三正丁氧基硅烷、仲丁基三仲丁氧基硅烷、仲丁基叔丁氧基硅烷、仲丁基三苯氧基硅烷、叔丁基三甲氧基硅烷、叔丁基三乙氧基硅烷、叔丁基三正丙氧基硅烷、叔丁基三异丙氧 Tri-n-propyl silane, n-propyl tri-sec-butoxy silane, n-propyl tert-butoxy silane, n-propyl triphenoxysilane, isopropyl trimethoxysilane, isopropyl triacetate silane, isopropyl tri-n-propoxysilane, isopropyl triisopropoxysilane, isopropyl tri-n-butoxy silane, isopropyl tri-sec-butoxy silane, isopropyl tert silane, triphenyl silane isopropyl, n-butyl trimethoxy silane, n-butyl triethoxysilane, tri-n-butyl-n-propoxy silane, n-butyl triisopropoxysilane, n tri-n-butyl baby alkoxy group, n-butyl tri-sec-butoxy silane, n-butyl tert-butoxy silane, triphenyl silane, n-butyl, sec-butyl trimethoxysilane, sec - i- triethoxysilane, tri-sec-propoxysilane, sec-butyl triisopropoxysilane, tri-sec-butoxy silane, sec-butyl tri-sec-butoxy silane, sec-butoxy tert-butoxy silane, sec-butyl triphenoxysilane, t-butyl trimethoxy silane, tert-butyl triethoxysilane, t-butyl tri-n-propoxy silane, t-butyl oxide triisopropoxide 硅烷、叔丁基三正丁氧基硅烷、叔丁基三仲丁氧基硅烷、叔丁基叔丁氧基硅烷、叔丁基三苯氧基硅烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、苯基三正丙氧基硅烷、苯基三异丙氧基硅烷、苯基三正丁氧基硅燒、苯基三仲丁氧基娃院、笨基叔丁氧基娃燒、苯基三苯氧基娃烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、Y-氨基丙基三甲氧基硅烷、Y -氨基丙基三乙氧基硅烷、Y-环氧丙氧基丙基三甲氧基桂烷、Y -环氧丙氧基丙基三乙氧基娃烷、Y-三氟丙基三甲氧基硅烷、Y-三氟丙基三乙氡基硅烷等。 Silane, tri-n-butoxy silane t-butyl, t-butyl tri-sec-butoxy silane, t-butyl-t-butoxy silane, t-butyl triphenoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane triethoxysilane, phenyl tri-n-propoxysilane, phenyl triisopropoxysilane, phenyl tri-n-butoxy silicon burning, phenyl tri-sec-butoxy baby hospital, tert-butoxy group baby stupid burning, phenyl group, trityl baby alkoxy, vinyltrimethoxysilane, vinyltriethoxysilane, Y- aminopropyl trimethoxy silane, Y - aminopropyl triethoxysilane, Y- ring oxopropoxy propyl trimethoxy Gui alkyl, Y - glycidoxypropyl triethoxy baby alkoxy, Y- trifluoropropyl trimethoxy silane, Y- trifluoropropyl triethyl silane radon Wait. 其中,优选甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三甲氧基硅烷、乙基三乙氧基硅烷等。 Of these, methyl trimethoxysilane, methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane and the like.

此外,式(2)中,R为 Further, the formula (2), R is

(7)碳原子数为16或以上的直链烷基; (7) a carbon number of 16 or greater straight chain alkyl;

(彳)可被取代且具有至少一个降冰片烷环的一价有机基团; (々)可被取代且具有至少一个甾体骨架的一价有机基团; (Left foot), and may be substituted by a monovalent organic group having at least one ring of norbornane; (々) may be substituted with at least one steroid skeleton a monovalent organic group;

(工)具有带有选自氟原子、三氟甲基以及三氟甲氧基的取代基的芳香环且碳原子数为8或以上的一价基团;或者(才)具有肉桂酰基或查耳酮基的感光性基团的化合物(以下称为化合物(B))可以列举例如十六烷基三甲氧基硅烷、十七烷基三甲氧基硅烷、十八烷基三甲氧基硅烷、十九烷基三甲氧基硅烷、十六烷基三乙氧基硅烷、十七烷基三乙氧基硅烷、十八烷基三乙氧基硅烷、十九烷基三乙氧基硅烷等(以上是R为(7)的化合物); (Work) having an aromatic ring selected from a fluorine atom, trifluoromethyl and trifluoromethoxy substituent groups and carbon atoms of 8 or more a monovalent group; or (only) having a cinnamoyl group or a check a photosensitive group compound chalcone group (hereinafter referred to as compound (B)) may include, for example, hexadecyl trimethoxysilane, heptadecyl trimethoxysilane, octadecyl trimethoxysilane, ten nine trimethoxysilane, hexadecyl triethoxysilane, heptadecyl triethoxysilane, octadecyl triethoxysilane, nonadecyl triethoxysilane (more R is (7) the compound);

R为选自下述式(4)〜(16)的结构的化合物(R为(彳)的化合物); R is (a compound wherein R is (left foot)) is selected from the following compounds of formula (4) to (16);

^-3_OH3 ⑷夺9h(3> 在(^) ^ CHf) ^ -3_OH3 ⑷ wins 9h (3> at (^) ^ CHf)

COO-C-CH3 H2C-C-CH3 F O-CF2CF2CF3 H2C-C-CH3 COO-C-CH3 H2C-C-CH3 F O-CF2CF2CF3 H2C-C-CH3

CHj CH3 CHj CH3

SiH(OCH2CH3)2 SiH (OCH2CH3) 2

R为选自下述式(17)〜(26)的结构的化合物(R为(々)的化合物); R is (R is a compound (々)) is selected from the following compounds of formula (17) to (26);

R为选自下述式(27)〜(30)的结构的化合物(R为(工)的化合物); (Compound R is a (work)) is selected from the following formulas (27) to the compound structure (30) is R;

4'-查耳酮基三甲氧基硅烷、4'-查耳酮基三乙氧基硅烷、肉桂酰基三甲氧基硅烷、肉桂酰基三乙氧基硅烷、肉桂酰氧基三甲氧基硅烷、肉桂酰氧基三乙氧基硅烷(以上是R为(才)的化合物)等。 Chalcone 4'-trimethoxy silane, a 4'-chalcone group triethoxysilane, trimethoxysilane cinnamoyl, cinnamoyl triethoxy silane, trimethoxy silane cinnamoyl, cinnamoyl acyloxy triethoxysilane (above R is (only) of the compound). 它们可以I种或者2种或以上同时使用。 They may be I or two or more kinds used in combination.

作为化合物(2),优选从上述化合物(A)和上述化合物(B)每一组选择一种或以上进行组合使用。 As the compound (2), preferably from the above-mentioned compound (A) and said compound (B) each group selecting one or more used in combination.

化合物(I)和化合物(2)的使用比率,相对于化合物(I)和(2)的总量,优选化合物(2)为10〜"摩尔。/。,更优选为50〜99摩尔%。 Compound (I) and compound (2) using a ratio, with respect to the compound (I) and the total amount of (2), preferably the compound (2) is 10~ "./ mol., More preferably 50~99 mol%.

反应产物(I)可以通过使化合物(1)、化合物(2)和水进行反应,使其水解.部分缩合而制得。 The reaction product (I) can be (1), the compound (2) and water by reacting a compound followed by hydrolysis. Partial condensation in the system. 为了使化合物(I)和化合物(2)水解、 To make Compound (I) and compound (2) is hydrolyzed,

部分缩合,每摩尔硅氧烷键(式(I)的-OR1与式(2)的-OR2的总和)优选使用1.0〜1.5摩尔水。 Partial condensation, (the sum of the formula (I) is -OR1 formula (2) is -OR2) is used per mole of siloxane bond preferably 1.0~1.5 moles of water. 当水的量达到I摩尔或以上时,硅氧烷键未反应的原样残留的可能性下降,没有涂膜均勾性下降的可能,并且,液晶定向剂保存稳定性下降的可能性也降低,因此是优选的。 When the amount of water reaches I molar or more, as is the possibility of remaining unreacted siloxane bonds decreased, no coating film properties are likely to decrease the hook, and the possibility of decreased storage stability of liquid crystal aligning agent also decreases, It is therefore preferred. 水可以断断续续或连续地加入到溶解有化合物(I)和化合物(2)的有机溶剂中。 Water may be continuously or intermittently added to dissolved the compound (I) and the compound (2) an organic solvent. 这时可以使用反应催化剂,当使用催化剂时,可以预先将催化剂加入到有机溶剂中,也可以在加入水时将其溶解或分散于水中。 Then you can use a reaction catalyst, when a catalyst, the catalyst may be previously added to the organic solvent, water may be added when dissolved or dispersed in water. 此时的反应温度,优选为O〜10(TC,更优选为15 〜801C。 The reaction temperature is preferably O~10 (TC, more preferably 15 ~801C.

使化合物(I)和化合物(2)水解、部分缩合时的有机溶剂,优选可以使用选自醇类溶剂、酮类溶剂、酰胺类溶剂、酯类溶剂和非质子类溶剂的至少I种溶剂。 Compound (I) and compound (2) is hydrolyzed partial condensation when the organic solvent, preferably selected from alcohols can be used solvents, ketone solvents, amide solvents, ester solvents and aprotic solvents, at least I solvents.

这里,作为醇类溶剂,可以列举例如曱醇、乙醇、正丙醇、 异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇、正戌醇、异戌醇、2-甲基丁醇、仲戌醇、叔戊醇、3-甲氧基丁醇、正己醇、2-甲基戌醇、仲己醇、2-乙基丁醇、仲庚醇、3-庚醇、正辛醇、2-乙基己醇、仲辛醇、正壬醇、2,6-二曱基-4-庚醇、正癸醇、仲十一烷醇、三曱基壬醇、仲十四烷醇、仲十七烷醇、苯酚、环己醇、曱基环己醇、3,3,5-三甲基环己醇、苄醇、二丙酮醇等一元醇类溶剂; Here, the alcohol solvents include e.g. Yue, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-isoamyl alcohol, isoamyl alcohol, 2- butanol, sec-isoamyl alcohol, tert-amyl alcohol, 3-methoxybutanol, n-hexanol, 2-methyl isoamyl alcohol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, octanol, n-nonanol, 2,6-Yue-4-heptanol, n-decanol, sec-undecyl alcohol, nonyl alcohol three Yue group, sec-ten tetracosanol, secondary heptadecanol, phenol, cyclohexanol, Yue cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, diacetone alcohol, a monohydric alcohol solvent;

乙二醇、1,2-丙二醇、1,3-丙二醇、2,4-戍二醇、2-甲基2,4-戌二醇、2,5-己二醇、2,4-庚二醇、2-乙基-1,3-己二醇、二甘醇、 Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,4-hexanediol Shu, Xu 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-pimelate alcohol, 2-ethyl-1,3-hexanediol, diethylene glycol,

一缩二丙二醇、三甘醇、三丙二醇等多元醇类溶剂; Dipropylene glycol, triethylene glycol, tripropylene glycol and other polyhydric alcohol solvents;

乙二醇单甲酸、乙二醇单乙醚、乙二醇单丙醚、乙二醇单丁基醚、乙二醇单己基醚、乙二醇单苯基醚、乙二醇单-2-乙丁基醚、二甘醇单曱醚、二甘醇单乙醚、二甘醇单丙醚、二甘醇单丁基醚、二甘醇、单己基醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单丙醚、丙二醇单丁基醚、一缩二丙二醇单甲醚、一缩二丙二醇单乙醚、一缩二丙二醇单丙醚等多元醇部分醚类溶剂;等等。 Ethylene glycol mono-carboxylic acid, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-acetate butyl ether, diethylene glycol monomethyl ether Yue, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol, monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether and other polyhydric alcohol portion of an ether solvent; and the like.

这些醇类溶剂可以I种或者2种或以上同时使用。 These alcohol solvents may be Type I or simultaneous use of two or more. 作为酮类溶剂,例如除了丙酮、甲基乙基酮、甲基正丙基酮、甲基正丁基酮、二乙基酮、甲基异丁基酮、甲基正戌基酮、乙基正丁基酮、甲基正己基酮、二异丁基酮、三甲基壬酮、环己酮、2_己酮、甲基环己酮、2,4-戌二酮、丙酮基丙酮、苯乙酮、葑酮等以外,还可以列举乙酰丙酮、2,4-己二酮、2,4-庚二酮、3,5-庚二酮、2,4-辛二酮、3,5-辛二酮、2,4-壬二酮、3,5-壬二酮、5-曱基-2,4-己二酮、2,2,6,6-四甲基-3,5-庚二酮、1,1,1,5,5,5-六氟-2,4-庚二酮等P -二酮类等。 Examples of the ketone solvent, for example in addition to acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n Xu ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, 2_ cyclohexanone, methyl cyclohexanone, 2,4 Xu dione, acetonyl acetone, except acetophenone, fenchone the like, it may also include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5 - octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-Yue-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5 hept-dione, 1,1,1,5,5,5-hexafluoro-2,4-heptane dione P - diketones.

这些酮类溶剂可以I种或者2种或以上同时使用。 These ketone solvents may be Type I or simultaneous use of two or more.

作为酰胺类溶剂,可以列举例如甲酰胺、N-甲基甲酰胺、N,N-二甲基甲酰胺、N-乙基甲酰胺、N,N-二乙基甲酰胺、乙酰胺、N-甲基乙酰胺、N,N-二甲基乙酰胺、N-乙基乙酰胺、N,N-二乙基乙酰胺、N-甲基丙酰胺、N-甲基吡咯烷酮、N-甲酰基吗啉、N-甲酰基哌啶、N-甲酰基吡咯烷、N-乙酰基吗啉、N-乙酰基哌啶、N-乙酰基吡咯烷等。 Examples of the amide solvents include formamide, N- methylformamide, N, N- dimethylformamide, N- ethyl formamide, N, N- diethylformamide, acetamide, N- dimethylacetamide, N, N- dimethylacetamide, N- ethyl acetamide, N, N- diethylacetamide, N- methyl propionamide, N- methylpyrrolidone, N--formyl morpholine, N- formyl piperidine, N- formyl pyrrolidine, N- acetyl-morpholine, N- acetyl piperidine, N- pyrrolidine and the like.

这些酰胺类溶剂可以I种或者2种或以上同时使用。 These amide solvents may be Type I or simultaneous use of two or more.

作为酯类溶剂,可以列举例如碳酸二乙酯、碳酸乙烯酯、碳酸丙缔酯、碳酸二乙酯、醋酸甲酯、醋酸乙酯、Y-丁内酯、Y-戌内酯、醋酸正丙酯、醋酸异丙酯、醋酸正丁酯、醋酸异丁酯、醋酸仲丁酯、醋酸正戌酯、醋酸仲戌酯、醋酸3-甲氧基丁酯、醋酸甲基戊酯、醋酸2-乙基丁酯、醋酸2-乙基己酯、醋酸苄酯、醋酸环己酯、醋酸甲基环己酯、醋酸正壬基酯、乙酰乙酸甲酯、乙酰乙酸乙酯、醋酸乙二醇单甲醚、醋酸乙二醇单乙醚、醋酸二甘醇单甲醚、醋酸二甘醇单乙醚、醋酸二甘醇单正丁基醚、醋酸丙二醇单甲醚、醋酸丙二醇单乙醚、醋酸丙二醇单丙醚、醋酸丙二醇单丁基醚、醋酸一缩二丙二醇单曱醚、醋酸一缩二丙二醇单乙醚、乙二醇二醋酸酯、甲氧基三甘醇醋酸酯、丙酸乙酯、丙酸正丁酯、丙酸异戌酯、草酸二乙酯、草酸二正丁酯、乳酸甲酯、乳酸乙 Examples of the ester solvents include diethyl carbonate, such as n, ethylene carbonate, propyl carbonate associative carbonate, diethyl carbonate, methyl acetate, ethyl acetate, Y- butyrolactone, Y- Xu lactone, propyl acetate acetate, isopropyl, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n Xu acetate, sec Xu acetate, 3-methoxybutyl acetate, methyl acetate, amyl acetate, 2- ethyl, butyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol mono acetate methyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol acetate, mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl acetate ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether Yue, acetate, dipropylene glycol monomethyl ether, ethylene glycol diacetate, methoxy triethylene glycol acetate, ethyl propionate, n butyl propionate, isoamyl acetate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate 酯、乳酸正丁酯、乳酸正戊酯、丙二酸二乙酯、酞酸二甲酯、酞酸二乙酯等。 Acrylate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.

这些酯类溶剂可以I种或者2种或以上同时使用。 These ester solvents may be Type I or simultaneous use of two or more.

作为非质子类溶剂,可以列举例如乙腈、二甲基亚砜、N,N,N'N'-四乙基磺酰胺、六甲基磷酸三酰胺、N-曱基吗啉(J手/U乇少水口乂)、N-甲基吡咯、N-乙基吡咯、N-甲基-A3-吡咯啉、N-甲基哌啶、N-乙基哌啶、N,N-二甲基哌嗪、N-甲基咪唑、N-甲基-4-哌啶酮、N-甲基-2-哌啶酮、N-甲基-2-吡咯烷酮、1,3-二甲基-2-咪唑啉酮、1,3-二甲基四氢-2(1H)-嘧啶酮等。 As the aprotic solvent, examples thereof include acetonitrile, dimethyl sulfoxide, N, N, N'N'- tetraethyl sulfamide, hexamethylphosphoric triamide, N- Yue morpholine (J Hand / U Torr outlet qe less), N- methylpyrrole, N- ethyl pyrrole, N- methyl -A3- pyrroline, N- methylpiperidine, N- ethylpiperidine, N, N- dimethylpiperazine piperazine, N- methylimidazole, N- methyl-4-piperidone, N- methyl-2-piperidone, N- methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone pyrazolone, 1,3-dimethyl-tetrahydro -2 (1H) - pyrimidinone like. 其中,特别优选多元醇类溶剂、多元醇部分醚类溶剂、酯类溶剂。 Among them, preferred polyhydric alcohol solvents, ether solvents polyol moiety, an ester solvent. 此外,在化合物(I)和化合物(2)的水解、部分缩合反应中,优选使用催化剂。 Further, the hydrolysis of the compound (I) and the compound (2), the partial condensation reaction, a catalyst is preferably used. 作为这种催化剂,可以列举以下的金属配合物、有机酸、无机酸、有机碱、无机碱。 As such catalyst, there may be mentioned metal complexes, organic acids, inorganic acids, organic bases and inorganic bases.

作为金属配合物,可以列举例如三乙氧基.单(乙酰丙酮)钦、三正丙氧基•单(乙酰丙酮)钬、三异丙氧基•单(乙酰丙酮)钦、三正丁氧基•单(乙酰丙酮)钦、三仲丁氧基.单(乙酰丙酮)钬、三叔丁氧基.单(乙酰丙酮)钛、二乙氧基•二(乙酰丙酮)钛、二正丙氧基•二(乙酰丙酮)钛、二异丙氧基.二(乙酰丙酮)钛、二正丁氧基.二(乙酰丙酮)钛、二仲丁氧基.二(乙酰丙酮)钦、二叔丁氧基.二(乙酰丙酮)钬、单乙氧基.三(乙酰丙酮)钦、单正丙氧基.三(乙酰丙酮)钦、单异丙氧基•三(乙酰丙酮)钦、单正丁氧基.三(乙酰丙酮)钦、单仲丁氧基•三(乙酰丙酮)钛、单叔丁氧基.三(乙醜丙明)钬、四(乙既丙酮)钬、 Examples of the metal complex may include triethoxysilane. Mono (acetylacetonate) Chin, • tri-n-propoxy mono (acetylacetonate) holmium, triisopropoxide • mono (acetylacetonate) Chin, tri-n-butoxy • group mono (acetylacetonate) Chin, tri-sec-butoxy. mono (acetylacetonate) holmium, tri-t-butoxy. mono (acetylacetonate) titanium, diethoxy • bis (acetylacetonato) titanium, di-n-propyl • oxy bis (acetylacetonate) titanium, diisopropoxy. bis (acetylacetonate) titanium, di-n-butoxy. bis (acetylacetonate) titanium, di-sec-butoxy. bis (acetylacetonate) Chin, two tert-butoxy. bis (acetylacetonate) holmium, monoethoxy. tris (acetylacetonate) Chin, mono-n-propoxy. tris (acetylacetonate) Chin, • mono-isopropoxy-tris (acetylacetonate) Chin, mono-n-butoxy. tris (acetylacetonate) Chin, • mono sec-butoxy tris (acetylacetonate) titanium, mono-tert-butoxy. tris (Chou propan-out) holmium, tetrakis (b both acetone) holmium,

三乙氧基.单(乙酰乙酸乙酯)钛、三正丙氧基•单(乙酰乙酸乙酯)钦、三异丙氧基•单(乙酰乙酸乙酯)钦、三正丁氧基•单(乙酰乙酸乙酯)钬、三仲丁氧基•单(乙酰乙酸乙酯)钦、三叔丁氧基•单(乙酰乙酸乙酯)钦、二乙氧基.二(乙酰乙酸乙酯)鈦、二正丙氧基•二(乙酰乙酸乙酯)钛、二异丙氧基.二(乙酰乙酸乙酯)钦、二正丁氧基.二(乙酰乙酸乙酯)钛、二仲丁氧基.二(乙酰乙酸乙酯)钛、二叔丁氧基'二(乙酰乙酸乙酯)钦、单乙氧基•三(乙酰乙酸乙酯)钦、单正丙氧基•三(乙酰乙酸乙酯)钦、单异丙氧基.三(乙酰乙酸乙酯)钬、单正丁氧基•三(乙酰乙酸乙酯)钛、单仲丁氧基•三(乙酰乙酸乙酯)钦、单叔丁氧基•三(乙酰乙酸乙酯)钛、四(乙酰乙酸乙酯)钬、单(乙酰丙酮)三(乙酰乙酸乙酯)钛、二(乙酰丙酮) Triethoxysilane. Mono (ethylacetoacetate) titanium, tri-n-propoxy • mono (ethylacetoacetate) Chin, triisopropoxide • mono (ethylacetoacetate) Chin, tri-n-butoxy • mono (ethyl acetoacetate) holmium, tris • sec-butoxy mono (ethylacetoacetate) Chin, • tri-t-butoxy mono (ethylacetoacetate) Chin, diethoxy. bis (ethylacetoacetate ) titanium, di-n-propoxy • bis (ethylacetoacetate) titanium, diisopropoxy. bis (ethyl acetoacetate) Chin, di-n-butoxy. bis (ethylacetoacetate) titanium, di-sec butoxy. bis (ethylacetoacetate) titanium, di-t-butoxy 'bis (ethylacetoacetate) Chin, • mono-ethoxy tris (ethylacetoacetate) Chin, • mono-n-propoxy tris ( ethyl acetoacetate) Chin, single isopropoxy. tris (ethylacetoacetate), holmium, • mono-n-butoxy tris (ethylacetoacetate) titanium, mono • sec-butoxy tris (ethylacetoacetate) Chin, • mono-t-butoxy tris (ethylacetoacetate) titanium, tetrakis (ethyl acetoacetate) holmium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) (乙酰乙酸乙酯)钬、三(乙酰丙酮)单(乙酰乙酸乙酯)钛等钦配合物; (Ethyl acetoacetate) holmium, tris (acetylacetonato) mono (ethylacetoacetate) titanium complex Chin;

三乙氧基•单(乙酰丙酮)锆、三正丙氧基.单(乙酰丙酮)锆、三异丙氧基.单(乙酰丙酮)锆、三正丁氧基.单(乙酰丙酮)锆、三仲丁氧基.单(乙酰丙酮)锆、三叔丁氧基.单(乙酰丙酮)锆、二乙氧基.二(乙酰丙酮)锆、二正丙氧基.二(乙酰丙酮)锆、二异丙氧基•二(乙酰丙酮)锆、二正丁氧基•二(乙酰丙酮)锆、二仲丁氧基•二(乙酰丙鲷)锆、二叔丁氧基• 二(乙酰丙酮)锆、单乙氧基•三(乙酰丙酮)锆、单正丙氧基.三(乙酰丙酮)锆、单异丙氧基.三(乙酰丙酮)锆、单正丁氧基.三(乙酰丙酮)锆、单仲丁氧基.三(乙酰丙酮)锆、单叔丁氧基.三(乙酰丙酮)锆、四(乙酰丙酮)锆、 • triethoxy mono (acetylacetonate) zirconium, tri-n-propoxy. Mono (acetylacetonate) zirconium triisopropoxide. Mono (acetylacetonate) zirconium, tri-n-butoxy. Mono (acetylacetonate) zirconium , tri-sec-butoxy. mono (acetylacetonate) zirconium, tri-t-butoxy. mono (acetylacetonate) zirconium, diethoxy. bis (acetylacetonate) zirconium, di-n-propoxy. bis (acetylacetonate) zirconium, diisopropoxy • bis (acetylacetonato) zirconium, di-n-butoxy • bis (acetylacetonato) zirconium, di-sec-butoxy • bis (acetyl propionyl bream) zirconium, di-t-butoxy • bis ( acetylacetonate) zirconium, • mono-ethoxy tris (acetylacetonate) zirconium, mono-n-propoxy. tris (acetylacetonato) zirconium, mono-isopropoxy. tris (acetylacetonato) zirconium, mono-n-butoxy group III. (acetylacetonate) zirconium, mono sec-butoxy. tris (acetylacetonato) zirconium, mono-t-butoxy. tris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium,

三乙氧基.单(乙酰乙酸乙酯)锆、三正丙氧基•单(乙酰乙酸乙酯)锆、三异丙氧基.单(乙酰乙酸乙酯)锆、三正丁氧基•单(乙酰乙酸乙酯)锆、三仲丁氧基.单(乙酰乙酸乙酯)锆、三叔丁氧基.单(乙酰乙酸乙酯)锆、二乙氧基.二(乙酰乙酸乙酯)锆、二正丙氧基.二(乙酰乙酸乙酯)锆、二异丙氧基•二(乙酰乙酸乙酯)锆、二正丁氧基• 二(乙酰乙酸乙酯)锆、二仲丁氧基.二(乙酰乙酸乙酯)锆、二叔丁氧基-二(乙酰乙酸乙酯)锆、单乙氧基-三(乙酰乙酸D酯)锆、单正丙氧基.三(乙酰乙酸乙酯)锆、单异丙氧基.三(乙酰乙酸乙酯)锆、单正丁氧基.三(乙酰乙酸乙酯)锆、单仲丁氧基.三(乙酰乙酸乙酯)锆、单叔丁氧基•三(乙酰乙酸乙酯)锆、四(乙酰乙酸乙酯)锆、单(乙酰丙酮)三(乙酰乙酸乙酯)锆、二(乙酰丙酮)二(乙酰乙酸乙酯 Triethoxysilane. Mono (ethylacetoacetate) zirconium, tri-n-propoxy • mono (ethylacetoacetate) zirconium triisopropoxide. Mono (ethylacetoacetate) zirconium, tri-n-butoxy • mono (ethylacetoacetate) zirconium, tri-sec-butoxy. mono (ethylacetoacetate) zirconium, tri-t-butoxy. mono (ethylacetoacetate) zirconium, diethoxy. bis (ethylacetoacetate ) zirconium, di-n-propoxy. bis (ethylacetoacetate) zirconium, diisopropoxy • bis (ethylacetoacetate) zirconium, di-n-butoxy • bis (ethylacetoacetate) zirconium, di-sec butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy - bis (ethylacetoacetate) zirconium, mono-ethoxy - tris (acetoacetate ester D) zirconium, mono-n-propoxy tris ( ethyl acetoacetate) zirconium, mono-isopropoxy. tris (ethylacetoacetate) zirconium, mono-n-butoxy. tris (ethylacetoacetate) zirconium, mono sec-butoxy. tris (ethylacetoacetate) zirconium, • mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethyl acetoacetate ester )锆、三(乙酰丙酮)单(乙酰乙酸乙酯)锆等锆配合物; ) Zirconium and tris (acetylacetonato) mono (ethylacetoacetate) zirconium and zirconium complexes;

三(乙酰丙酮)铝、三(乙酰乙酸乙酯)铝等铝配合物;等等。 Tris (acetylacetonato) aluminum, tris (ethylacetoacetate) aluminum complexes such as aluminum; and the like.

有机酸可以列举例如乙酸、丙酸、丁酸、戌酸、己酸、庚酸、辛酸、壬酸、癸酸、草酸、马来酸、甲基丙二酸、已二酸、癸二酸、没食子酸、酪酸、苯六甲酸、花生四締酸、2-乙基己酸、油酸、硬脂酸、亚油酸、亚麻酸、水杨酸、安息香酸、对氨基安息香酸、对甲苯磺酸、苯磺酸、一氣乙酸、二氣乙酸、三氯乙酸、三氟乙酸、甲酸、丙二酸、磺酸、酞酸、富马酸、柠檬酸、酒石酸等。 May include an organic acid such as acetic, propionic, butyric, Xu acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid association, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-amino benzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, acetic acid stretch, two gas acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.

无机酸可以列举例如盐酸、硝酸、硫酸、氢氟酸、磷酸等。 It can include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.

有机碱可以列举例如咕咬、咐•咯、略嗓.p比咯院、略淀、皮考啉、三甲胺、三乙胺、一乙醇胺、二乙醇胺、二甲基一乙醇胺、一甲基二乙醇胺、三乙醇胺、二氮杂二环辛燒(夕Tiffc" &夕口才夕7>)、二氮杂二环壬烷、二氮杂二环十一碳烯、氢氧化四甲基铵等。 The organic base may include, for example, cushions bite, slightly • commanded, pyrrole hospital .p voice slightly, a little starch, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl two ethanolamine, triethanolamine, diazabicyclooctane oct-burn (Xi Tiffc "& eloquent Xi Xi 7>), diazabicyclo nonane, diazabicyclo undecene, tetramethylammonium hydroxide, and the like.

无机碱可以列举例如氨、氢氧化钠、氢氧化钾、氢氧化钡、氢氧化钙等。 Inorganic bases include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide and calcium hydroxide.

这些催化剂中,优选金属配合物、有机酸、无机酸,更优选的可以列举钬配合物、有机酸。 These catalysts, metal complexes, organic acids, inorganic acids, and more preferably may include holmium complex, an organic acid. 它们可以I种或者2种或以上同时使用。 They may be I or two or more kinds used in combination.

上述催化剂的用量,相对于100重量份化合物(I)和化合物(2)的组合(以完全水解缩合物进行换算),优选为0.001〜10重量份,更优选为0.001〜I重量份。 The amount of the catalyst composition with respect to 100 parts by weight of the compound (I) and the compound (2) (in terms of completely hydrolyzed condensate was), preferably 0.001~10 parts by weight, more preferably 0.001~I parts by weight.

本发明的液晶定向剂由反应产物(I)溶于或分散于有机溶剂中而形成。 The liquid crystal aligning agent of the present invention is dissolved or dispersed in an organic solvent to form a reaction product (I).

有机溶剂使用下述式(3)表示的溶剂, Organic solvent using a solvent represented by the following formula (3),

其中,R3为甲基、乙基、正丙基、异丙基、正丁基或叔丁基,m为0或者1,而n为I、2或3。 Wherein, R3 is methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl group, m is 0 or 1, and n is I, 2 or 3.

这种有机溶剂具体实例可以列举乙二醇单甲醚、丙二醇单甲醚、乙二醇单乙醚、丙二醇单乙醚、乙二醇单正丙醚、丙二醇单正丙醚、乙二醇单异丙醚、丙二醇单异丙醚、乙二醇单正丁基醚、丙二醇单正丁基醚、乙二醇单叔丁基醚、丙二醇单叔丁基醚。 Specific examples of such organic solvents include ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, propylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, propylene glycol isopropyl ether, ethylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol t-butyl ether.

这些溶剂可以单独或者两种或以上混合使用。 These solvents may be used alone or in combination of two or more thereof. 此外,还可以联合使用不导致固体析出的量的难以溶解所用材料的不良溶剂。 Further, it may be used jointly not result in precipitation of a solid in an amount of poor solvent used is difficult to dissolve the material.

作为这种不良溶剂的具体实例,可以列举例如正戌烷、异戌烷、正己烷、异己烷、正庚烷、异庚烷、2,2,4-三甲基戌烷、正辛烷、异辛烷、环己烷、甲基环己烷、癸烷、双茂、苯、甲苯、二甲苯、均四甲苯、茚、四氢萘、十氢萘、角鲨烷、乙基苯、三甲基苯、甲基乙基苯、正丙基苯、异丙基苯、二乙基苯、异丁基苯、三乙基苯、二异丙基苯、正戊基萘、三甲基苯等烃类溶剂;甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇、正戌醇、异戊醇、2-甲基丁醇、仲戌醇、叔戌醇、3-甲氧基丁醇、正己醇、2-甲基戌醇、仲己醇、2-乙基丁醇、仲庚醇、3-庚醇、正辛醇、2-乙基己醇、仲辛醇、仲壬醇、2,6-二甲基-4•庚醇、正癸醇、仲十一烷基醇、三甲基壬醇、仲十四烷基醇、仲十五烷基醇、苯酚、环己醇、甲基环己醇、3,3,5-三甲基环己醇、 Specific examples of such poor solvent include, for example, n-pentane, iso-pentane, n-hexane, isohexane, n-heptane, iso-heptane, 2,2,4-trimethyl pentane, n-octane, iso-octane, cyclohexane, methylcyclohexane, decane, dicyclopentadiene, benzene, toluene, xylene, durene, indene, tetrahydronaphthalene, decahydronaphthalene, squalane, ethylbenzene, tris methylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentyl naphthalene, trimethylbenzene hydrocarbon solvents such as; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-isoamyl alcohol, isoamyl alcohol, 2-methylbutanol, sec-Xu alcohol, t-isoamyl alcohol, 3-methoxybutanol, n-hexanol, 2-methyl isoamyl alcohol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2 ethylhexanol, octanol, nonanol secondary, -4 • 2,6-dimethyl-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, secondary pentadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethyl cyclohexanol, 苄基醇、苯基甲基甲酵、双丙酮醇、甲苯酚等一元醇类溶剂;乙二醇、1,2-丙二醇、1,3-丁二醇、2,4-戌二醇、2-甲基-2,4-戌二醇、2,5-己二醇、2,4-二庚二醇、2-乙基-1,3•己二醇、二甘醇、一缩二丙二醇、三甘醇、三丙二醇、甘油等多元醇类溶剂;丙酮、甲基乙基酮、甲基正丙基酮、甲基正丁基酮、二乙基酮、甲基异丁基酮、甲基正戊基酮、甲基戊基酮、乙基正丁基酮、甲基正己基酮、二丙基酮、二异丙基酮、三甲基壬酮、环戌酮、环己酮、甲基环己酮、环庚酮、2,4-戊二酮、丙酮基丙酮、苯乙酮、葑酮等酮类溶剂;二乙基醚、二异丙基醚、二正丙基醚、二正丁基醚、二正己基醚、2-乙基己基醚、环氧乙烷、1,2-环氧丙烷、二氧杂戌环、4-甲基二氧戌环、二氧六环、二甲基二氧六环、苯乙醚、二苯醚、四氢呋喃、2-甲基四氢呋喃等醚类溶剂;碳酸二乙酯 Benzyl alcohol, phenyl methyl fermentation, diacetone alcohol, cresol and other monohydric alcohol solvent; ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-hexanediol Xu, 2 - Xu methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl -1,3 • hexanediol, diethylene glycol, dipropylene glycol , triethylene glycol, tripropylene glycol, glycerol, polyhydric alcohol solvents; acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl -n-amyl ketone, methyl amyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, dipropyl ketone, diisopropyl ketone, trimethyl nonanone, Xu cyclic ketone, cyclohexanone, methyl cyclohexanone, cycloheptanone, 2,4-pentanedione, acetonyl acetone, acetophenone, fenchone and other ketone solvents; diethyl ether, diisopropyl ether, di-n-propyl ether, di-n-butyl ether, di-n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, propylene oxide, dioxane ring Xu, Xu 4-methyl dioxane ring, dioxane , dimethyl dioxane, benzene, diethyl ether, diphenyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran and the like ether solvents; diethyl carbonate 碳酸丙烯酯、Y-丁内酯、Y-戌内酯、醋酸甲酯、醋酸乙酯、醋酸正丙酯、醋酸异丙酯、醋酸正丁酯、醋酸异丁酯、醋酸仲丁酯、醋酸正戌酯、醋酸仲戌酯、醋酸3-曱氧基丁酯、醋酸甲基戌酯、醋酸2-乙基丁酯、醋酸2-乙基己酯、醋酸苄酯、醋酸正己酯、醋酸环己酯、醋酸辛酯、醋酸戌酯、醋酸异戊酯、醋酸甲基环己酯、醋酸正壬基酯、乙酰乙酸甲酯、乙酰乙酸乙酯、醋酸乙二醇单甲醚、醋酸乙二醇单乙醚、醋酸乙二醇单丙醚、醋酸乙二醇单丁基醚、醋酸二甘醇单甲醚、醋酸二甘醇单乙醚、醋酸二甘醇单正丁基醚、醋酸丙二醇单甲醚、醋酸丙二醇单乙醚、醋酸丙二醇单丙醚、醋酸丙二醇单丁基醚、醋酸一缩二丙二醇单甲醚、醋酸一缩二丙二醇单乙醚、乙二醇二醋酸酯、甲氧基三甘醇醋酸酯、苯乙酸乙脂、3_甲氧基丙睃甲酯、三乙氧基丙酸乙酯、丙酸甲酯 Propylene carbonate, Y- butyrolactone, Y- Xu lactone, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n Xu acetate, sec Xu acetate, 3- Yue butyl group, methyl acetate, Xu acetate, ethyl butyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, ring hexyl acetate, octyl acetate, Xu acetate, isoamyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene acetate glycol monoethyl ether, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol acetate, mono-n-butyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, butyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, ethylene glycol diacetate, methoxy triethylene glycol acetate, acetic acid ester, Suo 3_ methoxypropionate, methyl triethoxysilane ethyl propionate, methyl propionate 、丙酸乙酯、丙酸正丙酯、丙酸异丙酯、丙酸正丁酯、丙酸异丁酯、丙酸异戌酯、丙酸苄酯、丙酸乙氧基乙酯、草酸二乙酯、草酸二正丁酯、乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸异丙酯、乳酸正丁酯、乳酸正戌酯、甲酸甲酯、甲酸乙酯、曱酸正丙酯、甲酸异丙酯、甲酸正丁酯、甲酸异丁酯、甲酸正戌酯、曱酸异戊酯、丁酸曱酯、丁酸乙酯、丁酸正丙酯、丁酸异丙酯、丁酸正丁酯、丁酸异丁酯、丙二酸二乙酯、酞酸二甲酯、酞酸二乙酯、丙酮酸乙酯等酯类溶剂;N-甲基甲酰胺、N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、乙酰胺、N-甲基乙酰胺、N,N-二甲基乙酰胺、N-甲基丙酰胺、N-甲基吡咯烷酮等酰胺类溶剂;甲碗醚、乙碗酸、嗔吩、四氢漆吩、二甲基亚砚、环丁砚、1,3-丙磺酸内酯等含硫类溶剂等。 , Ethyl propionate, n-propyl, isopropyl propionate, n-butyl propionate, isobutyl propionate, butyl propionate, isoamyl propionate, benzyl acetate, ethoxyethyl propionate, oxalate diethyl, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, n Xu esters, methyl, ethyl, n-propyl acid Yue ester, isopropyl, n-butyl formate, isobutyl formate, n-ester Xu, Yue isoamyl butyrate Yue acetate, ethyl butyrate, propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, diethyl malonate, dimethyl phthalate, diethyl phthalate, ester solvents such as ethyl pyruvate; N-dimethylformamide, N, N - dimethylformamide, N, N- diethylformamide, acetamide, N- dimethylacetamide, N, N- dimethylacetamide, N- methyl propionamide, N- methylpyrrolidone amide-based solvents; A bowl ether, acetic acid bowl, anger thiophene, tetrahydro-thiophene paint, dimethylmethylene Yan, Yan sulfolane, 1,3-propane sultone, etc. and sulfur-containing solvents. 这些不良溶剂相对于100重量份上述式(3)表示的有机溶剂,使用例如50重量份或以下,优选30重量份或以下。 These poor solvents with respect to 100 parts by weight of the above-described formula (3) is an organic solvent, for example, 50 parts by weight or less, preferably 30 parts by weight or less.

本发明的液晶定向剂还可以进一步添加下述p -二酮: The liquid crystal aligning agent of the present invention may be further added the following p - dione:

I种或者2种或以上的乙酰丙酮、2,4-己二酮、2,4-庚二酮、3,5-庚二酮、2,4-辛二酮、3,5-辛二酮、2,4-壬二酮、3,5-壬二酮、 I or one or two or more of acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione , 2,4-nonanedione, 3,5-nonanedione,

5-甲基-2,4-己二酮、2,2,6,6-四甲基-3,5-庚二酮、1,1,1,5,5,5-六氟-2,4-庚二酮等。 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptane dione, 1,1,1,5,5,5-hexafluoro -2, 4-heptyloxy-dione.

在本发明所得的液晶定向剂中,还可以进一步添加肢体状的硅石、胶体状的矾土、有机聚合物、表面活性剂等成分。 In the obtained liquid crystal aligning agent of the present invention, the shaped body may be further added silica, colloidal alumina, organic polymers, surfactants and the like ingredients.

所谓胶体状硅石,是指例如将高纯度二氧化硅分散于上述亲水性有机溶剂中的分散液,通常是平均粒径为5〜30mu,优选为10〜20mn,固体成分的浓度为10〜40重量%的分散液。 The so-called colloidal silica, for example, refers to a high-purity silica dispersed in the hydrophilic organic solvent dispersion, usually an average particle diameter 5~30mu, preferably 10~20mn, concentration of the solid content of 10~ 40% by weight of the dispersion. 这样的股体状硅石可以列举例如日产化学工血(株)制造的甲醇硅溶胶和异丙醇硅溶肢;触媒化成工业(株)制造的OSCAL等。 Such strand-like material may include silica sol such as methanol and isopropanol silica sol manufactured by Nissan Chemical limb blood work (strain) produced; Catalysts & Chemicals Industries (Ltd.) and the like manufactured OSCAL.

胶体状矾土可以列举日产化学工业(株)制造的氧化铝溶胶520、氧化铝溶胶100、氧化铝溶胶200;川研7 7 O > S力/U(株)制造的氧化铝透明溶胶、氧化铝溶胶10、氧化铝溶胶132等。 Colloidal alumina include Nissan Chemical Industries (Co., Ltd.) 520 alumina sol, alumina sol 100, 200 alumina sol; manufactured by Kawaken 7 7 O> S Force / U (KK) of the transparent alumina sol, silica 10 alumina sol, alumina sol 132 and the like.

有机聚合物可以列举例如具有聚环氧烷结构的化合物、具有糖链结构的化合物、乙烯酰胺类聚合物、(甲基)丙烯酸酯化合物、芳香族乙烯化合物、树枝状高分子(尹> K 7 —)、聚酰亚胺、聚酰胺酸、聚丙炔、聚酰胺、聚喹喔啉、聚噁二唑、含氟聚合物等。 The organic polymer may include a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, vinyl amide polymers, (meth) acrylate compounds, aromatic vinyl compounds, dendrimer (Yin> K 7 -), polyimide, polyamic acid, polyglycerol alkynyl, polyamides, polyquinoxaline, polyoxadiazole, fluoropolymers and the like.

表面活性剂可以列举例如非离子表面活性剂、阴离子类表面活性剂、阳离子类表面活性剂、两性表面活性剂等,进一步可以列举聚硅酮表面活性剂、聚环氧烷类表面活性剂、含氟表面活性剂等。 The surfactant may include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and further include silicone surfactants, polyalkylene oxide-based surfactants containing fluorine surfactants.

此外,从提高对基板表面粘附性的角度出发,本发明的液晶定向剂还可以包括含官能性硅烷的化合物或含环氧基的化合物。 Further, the angle of adhesion from the substrate surface to improve the liquid crystal aligning agent of the present invention may further comprise a functional silane-containing compound or epoxy group-containing compound. 这种含官能性硅烷的化合物可以列举例如3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、2-氨基丙基三甲氣基硅烷、2-氨基丙基三乙氧基硅烷、N-(2•氨基乙基)-3-氨基丙基三曱氧基硅烷、N-(2•氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、3-脲基丙基三甲氧基硅烷、3-脲基丙基三乙氧基硅烷、N-乙氧羰基-3-氨基丙基三甲氧基硅烷、N-乙氧羰基-3-氨基丙基三乙氧基硅烷、N-三乙氧硅烷基丙基三亚乙基三胺、N-三甲氧硅烷基丙基三亚乙基三胺、10-三甲氧硅烷基-1,4,7-三癸烷、10-三乙氧硅烷基-1,4,7-三癸烷、9-三甲氧硅烷基-3,6-二氮杂壬基乙酸酯、9-三乙氧硅烷基-3,6-二氮杂壬基乙酸酯、N-苄基-3-氨基丙基三甲氧基硅烷、N-苄基-3-氨基丙基三乙氧基硅烷、N-苯基-3-氨基丙基三甲氧基硅烷、N-苯基-3-氨基丙基三乙氧基硅烷、N-二(羟乙基)-3-氨基丙基三曱氧基硅烷、N-二( Such functional silane-containing compound include 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxy silane gas-yl, 2-aminopropyl triethoxysilane silane, N- (2 • aminoethyl) -3-aminopropyl triethoxy silane Yue, N- (2 • aminoethyl) -3-aminopropyl methyl dimethoxysilane, 3-ureidopropyl trimethoxy silane, 3-ureidopropyl triethoxysilane, N- ethoxycarbonyl-3-aminopropyl trimethoxysilane, N- ethoxycarbonyl-3-aminopropyl triethoxysilane silane, N- propyl triethoxysilane triethylene triamine, N- trimethoxysilyl propyl triethylene triamine, 10-trimethoxysilyl 1,4,7-decane, 10 - triethoxysilane group decane 1,4,7, 9-trimethoxysilyl-3,6-diazepin-nonyl acetate, 9-3,6-triethoxysilane azepin-nonyl acetate, N- benzyl-3-aminopropyl trimethoxysilane, N- benzyl-3-aminopropyl triethoxysilane, N- phenyl-3-aminopropyltrimethoxysilane silane, N- phenyl-3-aminopropyl triethoxysilane, N- bis (hydroxyethyl) -3-aminopropyl triethoxy silane Yue, N- bis ( 羟己基)-3-氨基丙基三乙氧基硅烷等。 Hydroxyhexyl) -3-aminopropyl triethoxysilane. 另外,含环氧基的化合物优选可以列举例如乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、三丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、新戌二醇二缩水甘油醚、1,6-己二醇二缩水甘油醚、甘油二缩水甘油醚、2,2-二溴新戌二醇二缩水甘油醚、1,3,5,6-四缩水甘油-2,4-己二醇、N,N,N',N'-四缩水甘油间苯甲二胺、1,3-:(N,N-二缩水甘油氨基甲基)环己烷、N,N,N',N'-四缩水甘油-4,4'-二氨基二苯基甲烷等。 Further, preferably the epoxy group-containing compound may include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, a new Xu glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether Xu, tetraaza glycidyl-2,4-hexanediol, N, N, N ', N'- tetraglycidyl benzyl glycerol diamine, 1,3 - :( N, N- diglycidyl aminomethyl) cyclohexane , N, N, N ', N'- tetraglycidyl-4,4'-diaminodiphenyl methane and the like.

本发明液晶定向剂中的反应产物(I)与溶剂的比率,从粘性、挥发性方面考虑进行选择,将反应产物(I)中所含硅原子换算成二氧化硅,液晶定向剂中反应产物(I)的比率(固体成分浓度)为使二氧化硅的浓度优选为0.01〜70重量%,更优选为0.05~60重量%、进一步优选为1~30重量%的比率。 Ratio of reaction product (I) of the liquid crystal aligning agent of the present invention and a solvent, the viscosity, selected in view of the volatile, the reaction product (I) as silica, in the liquid crystal aligning agent reaction product in terms of silicon atom (I) a ratio (solid content concentration) is the concentration of silica is preferably 0.01~70% by weight, more preferably 0.05 to 60% by weight, more preferably 1 to 30% by weight ratio. 本发明的液晶定向剂,如下所述,优选通过例如棍涂法、旋涂法、印刷法等涂布于基板上,接着通过对其进行加热千燥,形成作为液晶定向膜的涂膜,当固体成分浓度不足0.01重量%时,则该涂膜的膜厚度变得过小,会出现不能得到良好的液晶定向膜的情况,当固体浓度超过70重量%时,涂膜的膜厚度变得过大,会出现难以得到良好的液晶定向膜的情况,并且,液晶定向剂的粘度增大,会使其涂布性能变差。 The liquid crystal aligning agent of the present invention, as described below, for example, a coating bar coating method, a spin coating method, printing method or the like onto a substrate, followed by heating preferably subjected to dry in forming a liquid crystal alignment film, coating film, when the solid content concentration is less than 0.01% by weight, then the film thickness of the coating film becomes too small, there will not be the case to obtain a good liquid crystal alignment film when the solids concentration exceeds 70 wt%, the film thickness of the coating film becomes too large, the situation will be difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent increases, so that the coating properties will deteriorate.

本发明液晶定向剂中的溶剂(II)的比率,在总个溶剂中所占比率优选为I〜100重量%,更优选为30~100重量°/。 The liquid crystal aligning agent of the present invention, the ratio of the solvent (II) in a solvent in the total percentage is preferably I~100 wt%, more preferably 30 to 100 wt ° /. ,进一步优选为70〜100重量%。 , More preferably 70~100% by weight.

使用本发明的液晶定向剂,例如通过以下的方法可以制造液晶显示元件。 A liquid crystal aligning agent of the present invention, for example, a liquid crystal display device can be manufactured by the following method.

(I)通过例如辊涂法、旋涂法、印刷法、喷墨法等方法,将本发明的液晶定向剂涂布在设有形成图案的透明导电膜的基板面上,接着,通过对涂布面进行加热形成涂膜。 (I) by a method such as roll coating method, a spin coating method, a printing method, an inkjet method or the like, the liquid crystal aligning agent of the present invention is coated on the substrate surface with a transparent conductive film pattern, and then, the coating heating the fabric to form a coating. 涂布和加热工序中的环境气体可以在氮气、氦气、氩气等惰性气体中进行,可以进一步根据需要在混入氢气等还原性气体的氛围气体中进行。 Atmosphere and heating the coating step may be carried out in nitrogen, helium, argon, an inert gas, may be further mixed into the reducing gas such as hydrogen gas atmosphere according to need. 这里,基板可以使用例如浮法玻璃、钠钙玻璃等玻璃;聚对苯二甲酸乙酯、聚对苯二甲酸丁酯、聚醚砜、聚曱基丙烯酸甲酯、聚碳酸酯等塑料制透明基板。 Here, a glass substrate may be used, for example float glass, soda lime glass or the like; polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polymethyl methacrylate Yue, made of transparent polycarbonate plastic substrate. 基板一面上所设置的透明导电膜可以使用氧化锡(SnO2)制作的NESA膜(美国PPG公司注册商标)、氧化铟-氧化锡(In2O3-SnO2)制作的ITO膜等。 The transparent conductive film substrate may be provided on one surface of a tin oxide (SnO2) produced NESA film (a registered trademark of PPG Corporation), indium oxide - tin oxide (In2O3-SnO2) fabricated ITO film. 这些透明导电膜的形成可以采用光刻蚀法和预先使用掩膜的方法。 The transparent conductive film and a method of photolithography using a mask in advance may be employed. 在液晶定向剂的涂布时,为了改善基板表面和透明导电膜与涂膜的粘合性,还可以在基板的表面上预先涂布含官能性硅烷化合物、含官能性钦化合物等。 When applying the liquid crystal aligning agent, to improve adhesion of the substrate surface and the transparent conductive film coating may also be applied in advance containing silane compound on the functional surface of the substrate, Chin-containing functional compound. 涂布液晶定向剂后,加热温度为不导致基板材料变形的温度,优选为20〜300X:,更优选为120~300卩。 After coating the liquid crystal aligning agent, the heating temperature of the substrate temperature not to cause deformation of the material, preferably 20~300X :, more preferably 120 to 300 Jie. 作为加热处理的热源,可以列举例如热风干燥炉、红外线加热炉、加热板等。 Heat treatment as a heat source, for example, may include a hot air drying oven, infrared furnace, a hot plate. 形成的涂膜的厚度优选为0.001〜I in m,更优选为0.005〜0.5 mm。 The thickness of the coating film formed is preferably 0.001~I in m, more preferably 0.005~0.5 mm.

(2)此外,对所形成的涂膜表面进行表面打磨,可以对液晶定向角度进行控制。 (2) Further, the coating film formed on the surface of the polished surface can be controlled by the liquid crystal orientation angle. 此外,通过电磁辐射和粒子束撞击表面的步骤,也可以控制液晶定向角度。 Further, by electromagnetic radiation beam striking surface and the step, the angle of orientation of the liquid crystal can be controlled. 这里所用的粒子束可以用离子束、中性原子束、电子束、分子束和基本粒子束等。 As used herein the particle beam can be an ion beam, neutral atom beam, electron beam, molecular beam, and substantially particle beams. 照射能量、照射角度、照射时间可以根据液晶定向膜的种类和给予的预倾斜角度值进行适当的调节。 The irradiation energy, irradiation angle, irradiation time values ​​can be appropriately adjusted according to the kind of the liquid crystal alignment film and a pretilt angle of administration. 当使用离子束时,离子束的离子种类优选使用氮气、氦气、氩气、氖气等惰性气体的离子束。 When using an ion beam, the ion beam using the ion beam ion species is preferably an inert gas such as nitrogen, helium, argon, neon and the like. 此外,在离子束照射时或照射后,为了中和离子,优选提供电子。 Further, when the ion beam irradiation or after irradiation, in order to neutralize ions, preferably electronic.

使用离子束,使照射面具有液晶定向性能的方法在特开平11-271773号公报等中已经公开。 Ion beam, the irradiation surface has a crystal orientation property methods have been disclosed in JP-A No. 11-271773 and the like in. 但是,在该公报中,使用氢化金刚石状的碳(DLC)等共价结合性材料作为形成液晶定向层的物质,通过化学气相粘附等非水性气体环境粘附法形成液晶定向层,而不是以作为现有液晶定向层形成方法广泛应用的辊涂法、旋涂法、印刷法、喷墨法等涂布工序作为对象的。 However, in this publication, the use of hydrogenated diamond-like carbon (DLC), etc. covalently bound material as a material forming the liquid crystal alignment layer, the liquid crystal alignment layer is formed by chemical vapor adhering non-aqueous gaseous environment adhering method, not a coating step of roll coating method as conventional liquid crystal alignment layer is formed of a widely used method, a spin coating method, a printing method, an inkjet method or the like as an object. 由于本发明的液晶定向剂是以溶液状提供的,具有能够直接利用旋涂法、印刷法等现有的液晶定向膜涂布所用的装置的优点。 Since the liquid crystal aligning agent of the present invention is provided in form of a solution, an advantage can be utilized as a conventional liquid crystal alignment film spin coating method, a printing method and the like used in the apparatus.

作为对离子束有效的液晶定向剂的具体例子,包括在液晶定向刑中使用聚酰胺酸或可溶性聚酰亚胺的特开平8-313912号公报、特开平8-313913号公报、特开平8-313916号公报以及特开平11 - 237638号公报。 Specific examples of the effective ion beam liquid crystal aligning agent comprising a soluble polyamic acid or polyimide Laid-Open Publication No. 8-313912 liquid crystal orientation Punishment, Laid-Open No. 8-313913, JP-8- No. 313 916 and JP-Open 11-- No. 237,638. 对于如上所述经受光和热的严酷环境后或者长时间驱动后液晶定向性和残像特性,在本发明中通过使用硅类材料,能够实现现有聚酰胺酸或可溶性聚酰亚胺所不具有的良好性能。 After subjected to the harsh environment of light and heat long-time driving as described above or the liquid crystal orientation and afterimage characteristics, in the present invention, by using a silicon-based material, it is possible to achieve conventional polyamic acid or polyimide having no soluble good performance.

使用电子束,使照射面具有液晶定向性能的方法在特开平06-130389号公报等中已经公开。 Using an electron beam, so irradiation surface properties of liquid crystal orientation method is disclosed in Laid-Open Patent Publication No. 06-130389, and the like. 但是,由于在该公报中,也是使用现有的聚酰胺酸或可溶性聚酰亚胺作为形成液晶定向层的物质,因而难以形成如本发明中所公开的对于光和热电压残留率下降少的液晶定向层。 However, since in this publication, as the material forming the liquid crystal alignment layer, it is difficult to form as disclosed in the present invention for light and heat voltage is less residual rate decreased using conventional polyamic acid or soluble polyimide The liquid crystal alignment layer.

使用分子束、中性原子束、基本粒子束和电磁辐射,使照射面定向的方法在特开平10 - 96928号公报等中已经公开。 Molecular beam, neutral atom beam, a particle beam and electromagnetic radiation substantially, a method of irradiating the surface orientation Unexamined Patent 10 - 96928 Patent Publication No. been disclosed, and the like. 但是, but,

由于在该公报中也是使用现有的聚酰亚胺作为形成液晶定向层的物质,因而难以形成如本发明中所公开的对于光和热电压残留率下降少的液晶定向层。 Since the material is formed as a liquid crystal alignment layer, it is difficult to form a liquid crystal alignment layer for a voltage drop less residual rate of light and heat as disclosed in the present invention is the use of conventional polyimide in this publication.

在本发明所述液晶定向剂的使用中,使化合物(2)总体中的1.0~50摩尔%为其中R2为查耳酮基或肉桂酰基等感光性基团的化合物,通过照射紫外线等电磁辐射,可以控制液晶定向角度。 In using the liquid crystal aligning agent of the present invention, the compound (2) is generally 1.0 to 50 mol% of the compound where R2 or a chalcone group and a cinnamoyl group as a photosensitive group, by irradiation with electromagnetic radiation such as ultraviolet , the angle of orientation of the liquid crystal can be controlled. 此外,由本发明液晶定向剂形成的液晶定向膜,通过例如如特开平6- 222366号公报或特开平6 - 281937号公报中所公开的部分照射紫外线的方法,或者如特开平10 - 96928号公报中所公开的对液晶定向膜表面经过多步驟进行位置选择性地照射离子束的方法,或者如特开平11 - 242225号公报中所公开的通过设置控制定向方法的构造,能够改善液晶显示元件的视场特性。 The liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention, for example as Laid Open 6- No. 222 366 JP Patent Laid-open 6 - Methods of irradiation of ultraviolet rays No. 281937 gazette disclosed in, or, as Laid Open 10 - No. 96928 Publication as disclosed in the surface of the liquid crystal alignment film a method of regioselectively ion beam irradiation through a multi-step, or, as Laid open 11-- Publication No. 242,225 disclosed by setting the configuration of the control method of orientation, the liquid crystal display element can be improved field characteristics.

(3)制造2块如上所述的形成液晶定向膜的基板,在其中一块基板的周围边缘部位以适当的图案涂布热固化性的密封剂。 (3) producing a substrate for liquid crystal alignment film formed as described above 2, wherein a peripheral edge portion of the substrate in a suitable pattern of applied heat curable sealant. 使各自液晶定向膜中的液晶定向方向垂直或逆平行,使两块基板通过间隙(细胞间隙)相对放置,使两块基板贴合后,加热使密封剂固化。 The liquid crystal alignment direction of respective liquid crystal orientation film or anti-parallel to the vertical, so that the two substrates through a gap (cell gap) disposed opposite the two substrates after bonding, heat cure the sealing agent. 向基板表面和密封剂分割出的细胞间隙内注入填充液晶,封闭注入孔,形成液晶细胞。 Segmented the substrate surface, and the sealant is injected into the cell gap filled with liquid crystal, the injection hole is closed, the liquid crystal cell is formed.

从使两块基板贴合至液晶注入的工序可以使用液晶滴入方式,即ODF(OneDrop Fill)方式。 That the two substrates bonded to the liquid crystal injecting step, a liquid crystal dropwise manner, i.e., ODF (OneDrop Fill) from manner. 将涂布了液晶定向膜并赋予了上述液晶定向性能的单块基板以适当的图案涂布紫外线固化性密封剂,在必要部位滴入液晶后,使其与另一块基板贴合,利用紫外线使密封剂固化。 The coated liquid crystal alignment film and the liquid crystal orientation imparted performance monolithic substrate in a suitable pattern-coated ultraviolet-curable sealing agent, the liquid crystal dropwise necessary part, so that the other substrate bonded together by using UV rays curing the sealant. 紫外光照射不局限于整体曝光,可以采用掩膜曝光、扫描曝光等适当的方式。 UV irradiation is not limited to the overall exposure, the exposure mask may be employed, a scanning exposure or the like in an appropriate manner.

然后,在液晶细胞的外表面,即构成液晶细胞的各个基板的另一侧面上贴合偏振片,使其偏振方向与形成该基板另一面的液晶定向膜的液晶定向方向一'致或者垂直,制得液晶显示元件。 Then, the outer surface of the liquid crystal cell, i.e. the other side of each substrate constituting the liquid crystal cell is laminated to the polarizer, so that the polarization direction of the liquid crystal alignment direction of the liquid crystal alignment film of the other surface of the substrate is formed with a 'or vertical actuator, liquid crystal display element was obtained.

液晶可以列举向列型液晶和碟状型液晶,其中优选向列型液晶,可以使用例如希夫氏碱类液晶、氧化偶氮基类液晶、联苯类液晶、苯基环已烷类液晶、酯类液晶、三联苯类液晶、联苯基环已烷类液晶、嘧啶类液晶、二氧六环类液晶、双环辛烷类液晶、立方烷类液晶等。 The liquid crystal may include nematic liquid crystals and smectic liquid crystal, nematic liquid crystal being preferred, for example, Schiff bases may be used liquid crystal, azoxy-based liquid crystals, biphenyl-based liquid crystal, phenyl cyclohexane type liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane based liquid crystal, pyrimidine liquid crystal, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals. 此外,这些液晶中也可以添加例如氣化胆甾醇、胆甾醇壬酸酴、胆甾醇碳酸酯等胆甾型液晶和以商品名“C-15”、“CB-15” 夕公司制)销售的手性剂(力4 7 A剤)而进行使用。 Further, the liquid crystal may be added, for example, gasification of cholesterol, cholesteryl pelargonic acid yeast, cholesteryl carbonate cholesteric liquid crystal and the tradename "C-15", "CB-15" Tokyo Corporation) sold chiral agent (force 4 7 A Ji) in use.

并且,还可以使用癸氧基苯亚甲基-P-氨基-2-甲基丁基桂皮酸酯^ f / —卜)等强介电性液晶。 And may also be used -P- decyloxy benzylidene-amino-2-methylbutyl ester cinnamic ^ f / - Bu) ferroelectric liquid crystal and the like.

液晶细胞外表面贴合的偏振片可以列举将聚乙烯醇延伸定向同时吸收碘所得的称作为H膜的偏振膜夹在醋酸纤维保护膜中而制成的偏振片或者H膜本身形成的偏振片。 The outer surface of the liquid crystal cell of the polarizing plate bonded to the polyvinyl alcohol include extending orientation while absorbing the resulting iodine is referred to as a polarizing film sandwiched H films acetate protective film made of a polarizing plate or a film itself formed of H .

实施例 Example

以下通过实施例对本发明进行更具体的说明,但本发明只要不超出其要点,并不以任何方式局限于这些实施例。 Hereinafter, the present invention will be more specifically described embodiments, but the present invention without departing from its gist is not in any way limited to these examples. 其中,在下述实施例中,份都是指重量份. Wherein, in the following examples, parts refer to parts by weight.

合成例I Synthesis Example I

将106.3g甲基三乙氧基硅烷、6.82g十八烷基三乙氧基硅烷和12.67g四甲氧基硅烷溶于261.Ig乙二醇单丁基醚后,用实验室用搅拌机搅拌,使溶液温度稳定在60r。 After 106.3g of methyltriethoxysilane, 6.82 g of octadecyl triethoxysilane and tetramethoxysilane was dissolved in 12.67g 261.Ig ethylene glycol monobutyl ether, was stirred using a laboratory stirrer , the solution temperature stabilized at 60r. 接着将46.8g溶有1.06g马来酸的离子交换水经I小时加入到溶液中。 Then 46.8g 1.06g of maleic acid dissolved in ion-exchanged water was added over I hour to the solution. 然后,在60°C下反应4小时,得到435g以SiO2浓度换算反应产物(I)为10重量%的溶液。 Then, the reaction for 4 hours at 60 ° C, to give 435g in terms of SiO2 concentration of reaction product (I) is 10 wt% solution. 将该溶液冷却至室温后,在50°C下蒸发除去溶液中的甲醇、乙醇混合溶液,然后加入65.3g乙二醇单丁醚,用孔径为0.2pm的滤膜过滤,得到液晶定向剂(A)。 The solution was cooled to room temperature, evaporated at 50 ° C for methanol solution was removed, a mixed solution of ethanol, followed by addition of 65.3g ethylene glycol monobutyl ether, 0.2pm pore size membrane filter to obtain a liquid crystal aligning agent ( A).

合成例2 Synthesis Example 2

将106.3g甲基三乙氧基硅烷、6.64g I-三甲基硅烷基-3,3-二氟-4,4-二甲基降冰片烷和12.67g四甲氧基硅烷溶于260.8g乙二醇单丁基醚后,用实验室用搅拌机撹拌,使溶液温度稳定在60°C。 The 106.3g methyl triethoxysilane, 6.64g I- trimethylsilyl-3,3-difluoro-4,4-dimethyl norbornane and tetramethoxysilane was dissolved in 12.67g 260.8g after ethylene glycol monobutyl ether, Jiao stirred using a laboratory stirrer, the solution temperature was stabilized at 60 ° C. 接着将47.3g溶有1.07g马来酸的离子交换水经I小时加入到溶液中。 Then 47.3g 1.07g of maleic acid dissolved in ion-exchanged water was added over I hour to the solution. 然后,在60°C下反应4小时,得到430g以Si02浓度换算反应产物(I)为10重量%的溶液。 Then, the reaction for 4 hours at 60 ° C, to give 430g Si02 content equivalent reaction product (I) is 10 wt% solution. 将该溶液冷却至室温后,在501:下蒸发除去溶液中的曱醇、乙醇混合溶液,然后加入65.2g乙二醇单丁醚,用孔径为0.2Mm的滤膜过滤,得到液晶定向剂(B)。 The solution was cooled to room temperature, in 501: the solution was evaporated to remove alcohol Yue, a mixed solution of ethanol, followed by addition of 65.2g ethylene glycol monobutyl ether, 0.2Mm membrane filter with a pore size to obtain a liquid crystal aligning agent ( B).

合成例3 Synthesis Example 3

将106.3g甲基三乙氧基硅烷、5.79g 3-三甲基硅烷氧基胆甾烷和12.67g四甲氧基硅烷溶于262.2g乙二醇单丁基醚后,用实验室用撹拌机搅拌,使溶液温度稳定在6(TC。接着将46.5g溶有1.06g马来酸的离子交换水经I小时加入到溶液中。然后,在60TC下反应4小时,得到420g以Si02浓度换算反应产物(I)为10重量%的溶液。将该溶液冷却至室温后,在50°C下蒸发除去溶液中的曱醇、 乙醇混合溶液,然后加入65.5g乙二醇单丁醚,用孔径为0.2MH1的滤膜过滤,得到液晶定向剂(C)。 After 106.3g methyl triethoxysilane, 5.79g 3- trimethylsiloxy cholestane and tetramethoxysilane was dissolved in 12.67g 262.2g ethylene glycol monobutyl ether, stirred using a laboratory Jiao stirring with the solution temperature stabilized at 6 (TC. then 46.5g 1.06g of maleic acid dissolved ion-exchanged water was added over I hour to the solution. then, the reaction at 60TC 4 hours, to give a concentration of 420g Si02 converted to the reaction product (I) is 10 wt% solution. after the solution was cooled to room temperature, the solution was removed Yue, ethyl alcohol mixed solution was evaporated at 50 ° C, followed by addition of 65.5g ethylene glycol monobutyl ether, with an aperture 0.2MH1 to membrane filtration to obtain a liquid crystal aligning agent (C).

合成例4 Synthesis Example 4

将92.98g甲基三乙氧基硅烷、6.64g 4'-三甲基硅烷氧基查耳酮、6.82g十八烷基三乙氧基硅烷和12.67g四甲氧基硅烷溶于259.6g乙二醇单丁基醚后,用实验室用搅拌机搅拌,使溶液温度稳定在60X:。 The methyltriethoxysilane 92.98g, 6.64g 4'- trimethylsiloxy chalcone, 6.82g octadecyl triethoxysilane and tetramethoxysilane was dissolved in 12.67g 259.6g B after glycol monobutyl ether, was stirred using a laboratory stirrer, the solution temperature was stabilized at 60X :. 接着将49.4g溶有1.12g马来酸的离子交换水经I小时加入到溶液中。 Then 49.4g 1.12g of maleic acid dissolved in ion-exchanged water was added over I hour to the solution. 然后,在6(TC下反应4小时,得到430g以Si02浓度换算反应产物(I)为10重量%的溶液。将该溶液冷却至室温后,在501C下蒸发除去溶液中的甲醇、乙醇混合溶液,然后加入65.0g乙二醇单丁醚,用孔径为0.2pm的滤膜过滤,得到液晶定向剂(D)。比较合成例I Then, the reaction for 4 hours (at TC 6, to give 430g Si02 content equivalent reaction product (I) is 10 wt% solution. The solution was cooled to room temperature, the solution was removed in a mixed solution of methanol, ethanol was evaporated at 501C , followed by addition of 65.0g ethylene glycol monobutyl ether, 0.2pm pore size membrane filter to obtain a liquid crystal aligning agent (D). synthesis Comparative Example I

将218.1g(1.0摩尔)苯均四酸二酸酐和198.27g(l摩尔)4,4'-二氨基二苯甲烷溶于1600g N-甲基-2-吡咯烷酮后,使该溶液在20°C下反应6小时。 The 218.1g (1.0 mol) of pyromellitic anhydride and 198.27g (l mol) of 4,4'-diaminodiphenylmethane was dissolved in 1600g N- methyl-2-pyrrolidone, the solution was 20 ° C and reaction for 6 hours. 接着将所得反应溶液倒入大量过量的丙_中,使得反应产物沉淀,通过对反应产物进行分离•洗涂•干燥,得到400.3g聚酰胺酸聚合物。 Then the resultant reaction solution was poured into a large excess of propionic _ so that the reaction product is precipitated, the reaction products are separated by wash-coating • • dried to give 400.3g polyamic acid polymer. 将该聚合物溶于Y -丁内酯中,用孔径为为0.2 mm的滤膜过滤,得到固体成分浓度为4%的液晶定向剂(E)。 The polymer was dissolved in Y - butyrolactone, to 0.2 mm and a pore size of the membrane filter, to give a solid content concentration of 4% of the liquid crystal aligning agent (E).

液晶的定向性 The orientation of the liquid crystal

使液晶显示元件电压进行开启切断时,用显微镜观察液晶细胞中有无异常区域,当没有异常区域时评价为“良好”。 The liquid crystal display element voltage when turned off, the liquid crystal cell was observed with a microscope or absence of the abnormal region, when the region no abnormality was evaluated as "Good." 在液晶显示元件制成后立即进行下述的光照射、热处理,然后进行检测。 The liquid crystal display performs the following light irradiation, a heat treatment immediately after the member is made, and then detected. 液晶显示元件残像消除时间 The liquid crystal display element afterimage removing time

在70T的环境温度下给液晶显示元件施加叠加3.0V直流、6.0V交流(峰值-峰值)而得的30赫兹、3.0V矩形波20小时,在驱动液晶显示元件后,切断电压,目视测定直至残像消除所需的时间。 70T at ambient temperature is applied to the liquid crystal display element is superimposed DC 3.0V, 6.0V AC (peak - peak) obtained by 30 Hz, rectangular waves 3.0V 20 hours after driving the liquid crystal display element, the cutoff voltage was visually measured until the time required to eliminate afterimage.

液晶显示元件的电压残留率 The residual rate of the liquid crystal display element voltage

在167毫秒的时间跨度内给液晶显示元件施加5V的电压,电压施加时间为60微秒,测定从电压解除至167毫秒后的电压残留率。 The liquid crystal display in the time span of 167 ms 5V voltage is applied to the device, a voltage application time of 60 microseconds, the measurement voltage to the voltage released from the residual rate after 167 ms. 测定装置采用(株)東陽f夕二力制的VHR-I,在60t:下进行。 Assay device (strain) VHR-I Dongyang f Xi two force system, in 60t: carried out. 在液晶显示元件制成后立即进行下述的光照射、热处理,然后进行测定。 The liquid crystal display performs the following light irradiation, a heat treatment immediately after the member is made, and then measured. 光照射 Photoirradiation

液晶显示元件制成后,以金属尚化物灯为光源,对整个元件进行光照射。 After the liquid crystal display element is fabricated, a metal compound yet the lamp as a light source, light irradiation of the entire element. 使用滤光器选择照射波长为300 - 450nm的波段,以2J/cm2的能量进行照射。 Using a filter to select the wavelength of the irradiation 300-- band of 450nm, an energy 2J / cm2 is irradiated.

热处理 Heat Treatment

将所制造的液晶显示元件置于IOOiC的烘箱中放置3周后,取出来缓慢冷却至室温。 After the manufactured liquid crystal display device was placed in an oven IOOiC left for 3 weeks, and it was slowly cooled to room temperature.

实施例I Example I

采用旋涂机将液晶定向剂(A)涂布在带有ITO膜透明电极的玻璃基板的透明电极面上,在3001的热风中加热干燥30分钟,形成干燥平均膜厚度为700埃的涂膜。 Using a spin coater to a liquid crystal aligning agent (A) is coated, dried for 30 minutes in a hot air heated to 3001 in the transparent electrode side of a glass substrate, a transparent electrode with an ITO film, an average film thickness of a dried coating film 700 Å .

制作两块如上形成液晶定向膜的基板,向各基板的周边部位,通过丝网印刷法涂布含有氧化铝球环氧树脂类粘合剂,将两块基板通过间隙使涂膜面相对放置,使周边部位之间对接压合,使粘合剂固化。 Making two substrates for liquid crystal alignment film formed as described above, the peripheral portion of each substrate by screen printing a coating comprising an epoxy resin adhesive containing aluminum oxide spheres, by two substrates placed opposite the gap so that the coated surface, abutment nip between the peripheral portion, to cure the adhesive. 向基板表面和周边部位粘合剂分割成的细胞间隙内,注入填充负性向列型液晶,然后,用环氧类粘合剂将注入孔封闭,制得垂直定向型液晶显示元件。 Of the adhesive into the substrate surface and the peripheral parts of the cell gap, injecting a negative nematic liquid crystal is filled, and then, using an epoxy adhesive injection hole is closed, to prepare a vertical alignment type liquid crystal display device.

对如上所得的刚刚制好的液晶显示元件,进行液晶定向性观察和电压残留率测定。 Just a good system to display the liquid crystal element obtained as described above, the liquid crystal orientation was observed and the residual voltage for determination. 准备3件用液晶定向剂(A)如上制造的液晶显示元件,一件进行光照,然后进行液晶定向性观察和电压残留率测定,另一件进行热处理,然后进行液晶定向性观察和电压残留率测定,剩下的一件按照所述方法测到残像消除时间。 3 prepared with liquid crystal aligning agent (A) as a display device for producing, for a light, and then the liquid crystal orientation was observed and the residual voltage for determination, the other heat treatment, and then the liquid crystal orientation was observed and the residual voltage ratio determination, a remaining measured according to the method of the afterimage removing time. 结果如表I所示。 The results are shown in Table I. 实施例2~3 Example 2-3

用合成例2〜3中所得的液晶定向剂,与实施例I同样地搮作制造液晶显示元件。 Obtained in Synthesis Example 2 or 3 of the liquid crystal aligning agent, in the same manner as in Example I for manufacturing a liquid crystal display element Li. 将每个所得的液晶显示元件,如实施例I所示对液晶定向性、电压残留率、残像消除时间进行评价。 Each of the resulting liquid crystal display device, as shown in Example I of the liquid crystal alignment property, the residual voltage ratio, the afterimage removing time was evaluated. 结果如表I所示。 The results are shown in Table I.

实施例4 Example 4

采用旋涂机将液晶定向剂(A)涂布在带有ITO膜透明电极的玻璃基板的透明电极面上,在300X:的热风中加热干燥30分钟,形成干燥平均膜厚度为700埃的涂膜。 Using a spin coater to a liquid crystal aligning agent (A) is applied, the surface of the transparent electrode 300X transparent electrode glass substrate with an ITO film: hot air heated and dried for 30 minutes, the average film thickness of a dried coating of 700 Å membrane.

通过200V的加速电压从与基板成40度角度的方向对该膜照射10秒钟氩离子束。 Beam irradiating the film with 10 seconds of argon ions from the substrate into the 40 degree angle with the direction of an accelerating voltage of 200V.

然后,将两块经离子束处理的液晶容纳基板的具有液晶定向膜的各自周边,通过丝网印刷法涂布添加了直径为5.5 Jiim的氧化铝球的环氧树脂类粘合剂,然后使两块液晶容纳基板的两液晶定向膜面相对放置,并使其与离子束照射方向垂直而进行重叠压合,使得粘合剂固化。 Then, the liquid crystal by two ion beam treatment of the periphery of each receiving liquid crystal alignment film having a substrate, an epoxy-based adhesive is added 5.5 Jiim diameter alumina balls is applied by a screen printing method, then two receiving two liquid crystal alignment film surface of a liquid crystal substrate is placed opposite, and it is perpendicular to the ion beam irradiation direction nip overlap, such that the adhesive cures.

接着通过液晶注入口向两块基板之间填充向列型液晶(j /U夕公司制,MLC- 6221),然后用丙烯酸类光固化粘合剂封闭液晶注入口,在基板的两外侧面上贴合偏振片,使偏振片偏振方向与各自基板的液晶定向膜的离子束照射方向一致,制得液晶显示元件。 Then the liquid crystal injection port (U Xi Corporation j /, MLC- 6221) between the two substrates is filled nematic liquid crystal and a photocurable acrylic pressure-sensitive adhesive with a liquid crystal injection port is closed, the outer surfaces of the two substrates bonding a polarizing plate, the polarizing plate so that the polarization direction of the ion beam coincides with a respective liquid crystal alignment film direction of the substrate, the liquid crystal display element was obtained.

将如此制得的每个液晶显示元件,如实施例I所示对液晶定向性、电压残留率、残像消除时间进行评价。 Each liquid crystal display element thus prepared, as in Example I embodiment shown in the liquid crystal orientation, the residual voltage ratio, the afterimage removing time was evaluated. 结果如表I所示。 The results are shown in Table I.

实施例5〜6采用合成例2~3所得的液晶定向剂,与实施例4同样地操作制造液晶显示元件。 Synthesis Examples 5 to 6 Example 2-3 using the liquid crystal aligning agent obtained in Example 4 was produced in the same manner as the liquid crystal display device. 将每个所得的液晶显示元件,如实施例I所示对液晶定向性、电压残留率、残像消除时间进行评价。 Each of the resulting liquid crystal display device, as shown in Example I of the liquid crystal alignment property, the residual voltage ratio, the afterimage removing time was evaluated. 结果如表I所示。 The results are shown in Table I.

实施例7 Example 7

采用旋涂机将液晶定向剂(D)涂布在带有ITO膜透明电极的玻璃基板的透明电极面上,在300X:的热风中加热干燥30分钟,形成干燥平均膜厚度为700埃的涂膜。 Using a spin coater liquid crystal aligning agent (D) is applied, at 300X with the transparent electrode side of a glass substrate having a transparent electrode of ITO film: hot air heated and dried for 30 minutes, the average film thickness of a dried coating of 700 Å membrane.

采用Hg-Xe灯,通过硬质(ZU 'y 只)(注册商标)玻璃制的偏振片SPF- 50C- 32(夕夂文光机制)切断320nm的短波长光,从基板面法线方向对该涂膜表面照射l.OJ/cm2以365nm为主的直线偏振光。 Using Hg-Xe lamp, by hard (ZU 'y only) polarizer (registered trademark) glass of SPF- 50C- 32 (Xi Fan mechanism described light) cutting a short wavelength light of 320nm, to a direction normal to the substrate the surface coating film is irradiated l.OJ / cm2 at 365nm oriented linearly polarized light.

制造两块如上照射处理的形成液晶定向膜的基板,在各块基板周边部位,通过丝网印刷法涂布含有氧化铝球环氧树脂类粘合剂,然后将两块基板通过间隙进行重合,使其与照射的紫外线偏振面方向相互平行,将周边部位对接压合,使粘合剂固化。 The substrate is formed two liquid crystal alignment film produced above irradiation treatment, the peripheral portion of the substrate in each block, by applying a screen printing method epoxy adhesive containing alumina balls, and then the two superposed substrate by a gap, UV irradiation plane of polarization directions parallel to each other so that the peripheral portion abutting nip, to cure the adhesive. 向基板表面和周边部位粘合剂分割成的细胞间隙内,填充向列型液晶(> A夕公司制,MLC- 6221),然后,用环氧类粘合剂将注入孔封闭,制得液晶显示元件。 Of the adhesive into the substrate surface and the peripheral parts of the cell gap is filled nematic liquid crystal (> A Xi Corporation, MLC- 6221), and then, using an epoxy adhesive injection hole is closed, the liquid crystal was prepared display element.

将每个如此制得的液晶显示元件,如实施例I所示对液晶定向性、电压残留率、残像消除时间进行评价。 Each of the thus prepared liquid crystal display device, as shown in Example I of the liquid crystal alignment property, the residual voltage ratio, the afterimage removing time was evaluated. 结果如表I所示。 The results are shown in Table I.

比较实施例I Comparative Example I

采用旋涂机将比较合成例I中所得液晶定向剂(E)涂布在带有ITO膜透明电极的玻璃基板的透明电极面上,在200X:的热风中加热干燥20分钟,形成千燥平均膜厚度为600埃的涂膜。 Using a spin coater obtained in Comparative Synthesis Example I crystal aligning agent (E) is coated with a transparent electrode side of a glass substrate, an ITO film as the transparent electrode, 200X: heating a hot-air dried 20 minutes to form the mean was dry a film thickness of 600 Å coating.

具有缠有人造纤维制的布的辊的打磨机对该涂膜进行打磨处理,搞的旋转速度为400rpm,段(只亍一夕)移动速度为3 Omm/秒,绒毛压入长度为0_4mm。 Sander having a wound with a cloth made of synthetic fibers of the coating film roll grinding process, the rotational speed of 400 rpm to engage, section (only the right foot overnight) a moving speed 3 Omm / sec, the length of villi pressed 0_4mm.

将每个如此制得的液晶显示元件,如实施例I所示对液晶定向性、电压残留率、残像消除时间进行评价。 Each of the thus prepared liquid crystal display device, as shown in Example I of the liquid crystal alignment property, the residual voltage ratio, the afterimage removing time was evaluated. 结果如表I所示。 The results are shown in Table I.

__表I __ Table I __ __

Claims (7)

  1. 1.一种液晶定向剂,其特征在于包括: (I)下述式(I)表示的硅化合物、下述式(2)表示的硅化合物和水的反应产物,以及(II)下述式(ί)表示的溶剂, Si(OR1)4..................(I) 其中R1为从曱基、乙基、丙基和丁基中选出的一价有机基团, RSi(OR2)3..................(2) 其中R为一价有机基团,而R2为从曱基、乙基、丙基和丁基中选出的一价有机基团, CH3 I R3O (CH) m (CH2) n0H ..........(3) 其中,R3为曱基、乙基、正丙基、异丙基、正丁基或叔丁基,m为I,而η为2或3, 并且,上述式(2)表示的硅化合物为下述硅化合物(A)与硅化合物(B)的混合物: (A)上述式(2)中R为任选可被选自氨基、环氧丙氧基和三氟曱基的取代基取代的CI〜4的烷基、乙烯基或苯基的硅化合物, (B)上述式(2)中R为如下基团的硅化合物: (a)碳原子数为16或以上的直链烷基; (b)具有降冰片烷环且选自下述式(4)〜(16) 1. A liquid crystal aligning agent, characterized by comprising: a silicon compound (I) represented by the following formula (I), the reaction product represented by the following formula (2) a silicon compound and water, and (II) by the following formula solvent (ί) represented by, Si (OR1) 4 .................. (I) wherein R1 is from ethyl, propyl and butyl groups selected Yue a monovalent organic group, RSi (OR2) 3 .................. (2) wherein R is a monovalent organic group, and R2 is a group from Yue, ethyl group, a monovalent organic group selected from propyl and butyl, CH3 I R3O (CH) m (CH2) n0H .......... (3) wherein, R3 is a group Yue, b group, n-propyl, isopropyl, n-butyl or tert-butyl group, m is I, and η is 2 or 3, and a silicon compound represented by the formula (2) by the following silicon compounds (a) and silicon a mixture of the compound (B) is: (a) the above-described formula (2) wherein R is an optionally substituted amino group may be selected from alkyl, glycidoxy group and trifluoromethoxy group substituted Yue CI~4 of vinyl phenyl or a silicon compound, (B) the above-described formula (2) wherein R is a silicon compound of the following groups: (a) number of 16 or more carbon atoms, straight-chain alkyl group; (b) having a norbornane ring and selected from the following formulas (4) to (16) 一价有机基团; A monovalent organic group;
    (c)具有甾体骨架且选自下述式(I7)〜(26)的一价有机基团; (C) having a steroidal skeleton and selected from the following formulas (I7) ~ (26) is a monovalent organic group;
    (d)具有芳香环且碳原子数为8或以上的选自下述式(27)〜(30)的一价有机基团; (D) a aromatic ring and a carbon number of 8 or more to (30) is a monovalent organic group selected from the following formulas (27);
    或者(e)具有肉桂酰基或查耳酮基的感光性基团。 Or (e) having a cinnamoyl group or chalcone group, a photosensitive group.
  2. 2.权利要求I所述的液晶定向剂,其中上述式(2)表示的化合物中,式(2)中R为感光性基团(e)的化合物占I〜50摩尔%。 The liquid crystal aligning agent according to claim I, a compound of the formula (2) wherein in the formula (2), R representing mole% I~50 a photosensitive group is a compound of (e).
  3. 3. —种液晶定向膜的形成方法,其特征在于包括将权利要求I或2所述的液晶定向剂涂布于基板的工序,和加热涂布的基板固化涂膜的工序。 3. The - method for forming a liquid crystal alignment film, characterized by comprising the liquid crystal aligning agent I or claim 2, a step of applying the substrate, and a cured coating film coated substrate heating.
  4. 4. 一种控制液晶定向角度的液晶定向膜的形成方法,其特征在于对权利要求3所述的液晶定向膜的膜表面进行打磨处理。 A method for forming a liquid crystal alignment film to control orientation angle of the liquid crystal, wherein the film surface of the liquid crystal alignment film 3, the sanding process the claim.
  5. 5. —种控制液晶定向角度的液晶定向膜的形成方法,其特征在于用选自X射线和紫外线的电磁辐射、选自离子束、中性原子束、电子束、分子束和基本粒子束的粒子束、或者电磁辐射和粒子束两者一起对权利要求3所述的液晶定向膜的膜表面进行照射。 5. - The method of forming a liquid crystal alignment film seed orientation angle of liquid crystal is controlled, characterized by electromagnetic radiation selected from X-rays and ultraviolet rays, selected ion beam, neutral atom beam, electron beam, molecular beam and the basic beam beam, and the beam of electromagnetic radiation or both membrane surfaces with the liquid crystal alignment film 3 is irradiated with the claims.
  6. 6.通过权利要求3〜5任意一项所述的方法制造的液晶定向膜。 By any of claims 3 to 5 6. The liquid crystal alignment film manufacturing method according to.
  7. 7. —种液晶显示元件,其特征在于具有权利要求6所述的液晶定向膜。 7. - kind of the liquid crystal display element, characterized by a liquid crystal alignment film of claim 6.
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