KR20140005765A - Liquid crystal aligning agent and liquid crystal display device - Google Patents

Abstract

(식 (1) 중, R1은 적어도 2개의 단환 구조를 갖는 기이고; R2는 2중 결합, 3중 결합, 에테르 결합, 에스테르 결합 또는 산소 원자를 포함하는 연결기이고; a는 0∼1의 정수임).(Problem) The liquid crystal display element of IPS and FFS system provided with the liquid crystal aligning agent which can form the liquid crystal display element of IPS and FFS system excellent in the agent characteristics, such as high-speed response, and this liquid crystal aligning agent. And it aims at providing the manufacturing method of such a liquid crystal display element.
(Solution means) This invention is a liquid crystal aligning agent for liquid crystal aligning film formation in the liquid crystal display element of IPS and FFS system, Comprising: The compound which has group represented by [A] following formula (1) (hereinafter, "[A] compound Also referred to as "

(In formula (1), R1 is a group having at least two monocyclic structures; R2 is a linking group containing a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom; a is an integer from 0 to 1) ).

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent and a liquid crystal display element,

This invention relates to the liquid crystal aligning agent, a liquid crystal display element, and the manufacturing method of a liquid crystal display element.

In recent years, liquid crystal display devices have advantages such as low power consumption, easy downsizing and flattening, and thus have a wide range of applications from small liquid crystal display devices such as mobile phones to large screen liquid crystal display devices such as liquid crystal televisions. Is being applied.

As the driving mode of the liquid crystal display device, TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), FFS (Fringe Field Switching), VA (Vertical Alignment) and the like are known.

In these driving modes, an electrode pair is arranged in a comb-tooth shape in one substrate surface, so that the driving direction of the liquid crystal when the electric field is applied is only in the substrate surface direction, and an IPS type electrode. It is known that the FFS (Fringe Field Switching) type liquid crystal display device having a change in structure and increasing the aperture ratio of the display element portion has excellent viewing angle characteristics (Japanese Patent Laid-Open No. 56-91277, US Patent No. 5,928,733, See Japanese Patent Application Laid-Open No. 2008-216572). Moreover, since liquid crystal is always oriented parallel with respect to a board | substrate, it is known that there is little liquid-crystal disturbance by the pressure from the outside, and display defects, such as an unevenness, are hard to produce. For this reason, the application of the IPS and FFS systems to applications such as mobile phones and tablet PCs with a touch panel function is expanding.

However, in recent years, mobile phones and tablet PCs have been used as video display devices, and as a characteristic required for liquid crystal display devices, further speeding up of the liquid crystal response speed is required so that afterimages can be suppressed as much as possible while smoothly displaying video. have.

Japanese Laid-Open Patent Publication No. 56-91277 US Patent No. 5,928,733 Japanese Laid-Open Patent Publication No. 2008-216572

This invention is made | formed based on the above circumstances, The liquid crystal aligning agent which can form the liquid crystal display element of the IPS and FFS system excellent in liquid crystal responsiveness, satisfying the liquid crystal aligning property generally requested | required as a liquid crystal display element, It aims at providing the liquid crystal display element of the IPS and FFS system provided with the liquid crystal aligning film formed from this liquid crystal aligning agent.

According to an aspect of the present invention,

As a liquid crystal aligning agent for liquid crystal aligning film formation in the liquid crystal display element of IPS and FFS system,

[A] It is characterized by containing a compound having a group represented by the following formula (1) (hereinafter also referred to as "[A] compound"):

(In formula (1), R ¹ is a group having at least two monocyclic structures; R ² is a linking group containing a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom; a is 0 to 1) Is an integer of).

The said liquid crystal aligning agent contains the [A] compound provided with the said group which has dielectric anisotropy, and is excellent in the orientation controllability of a liquid crystal molecule. For this reason, the liquid crystal display element of the IPS and FFS system provided with the liquid crystal aligning film formed using the said liquid crystal aligning agent has favorable orientation of liquid crystal molecules, and can shorten a response time.

[A] The compound is

A part derived from a polyorganosiloxane having an epoxy group,

What is necessary is just to have the part derived from the compound (it is also called a "specific carboxylic acid" hereafter) which has a carboxyl group represented by following formula (2):

(In formula (2), R <^1> , R <^2> and a are the same meaning as said Formula (1); R <^3> is a methylene group or a C2-C30 alkylene group, a phenylene group, or a cyclohexylene group, These The group may further have a substituent).

According to the said liquid crystal aligning agent, by using the reactivity of an epoxy group and a carboxyl group, the structure which has dielectric anisotropy represented by said Formula (1) as a side chain to polyorganosiloxane as a main chain as [A] compound can be easily introduce | transduced. have. Therefore, the said liquid crystal aligning agent can provide high speed responsiveness effectively to the liquid crystal display element obtained.

Said R <^1> should just be group represented by following formula (3):

(In formula (3), R ⁴ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group or an alkoxy group; R ⁵ and R ⁷ are each independently a phenylene group, a biphenylene group, naphthalene group, a cyclohexylene group, a bi-cyclohexylene group, a cyclohexylene group and the phenyl or heterocyclic ring, these groups may further have a substituent; R ⁶ is an alkylene group, a double bond of 1 to 10 carbon atoms, 3 A linking group including any of a heavy bond, an ether bond, an ester bond, and a heterocycle, and these groups may further have a substituent; b is an integer of 1 to 9; when b is 2 or more, a plurality of R ⁴ are the same C is an integer of 0-1, d is an integer of 1-2, and when d is 2, some R <^6> and R <^7> may be same or different, respectively).

By introducing the structure represented by said formula (3) to the [A] compound of the said liquid crystal aligning agent, the response of the liquid crystal display element obtained can be made faster.

The epoxy group may be a group represented by the following formula (X ¹ -1) or (X ¹ -2):

(In formula (X ^1-1 ), A is an oxygen atom or a single bond; h is an integer of 1 to 3; i is an integer of 0 to 6; provided that when i is 0, A is a single bond; ; formula (X ¹ -2) of the, j is an integer of 0 to 6).

In [A] compounds of the inclusion of the polyorganosiloxane group represented by the formula (X ¹ -1) or (X ¹ -2), the art liquid crystal aligning agent, it becomes easier to introduce a group represented by the above formula (1) .

The liquid crystal aligning agent may further contain at least one polymer (hereinafter also referred to as "[B] polymer") selected from the group consisting of [B] polyamic acid and polyimide. When a liquid crystal aligning film is formed using the liquid crystal aligning agent containing the [B] polymer, the liquid crystal display element with more improved liquid-crystal orientation can be obtained.

The liquid crystal display element of this invention is a liquid crystal display element of the IPS and FFS system provided with the liquid crystal aligning film formed from the said liquid crystal aligning agent. According to the said liquid crystal display element, by forming a liquid crystal aligning film with the said liquid crystal aligning agent, liquid crystal alignability is high and can exhibit the outstanding high-speed response.

As described above, according to the liquid crystal aligning agent of this invention, the liquid crystal display element of the IPS and FFS system excellent in the agent characteristics, such as high-speed response, can be formed. Moreover, the liquid crystal display element of this invention can exhibit high responsiveness etc. as an element of IPS and FFS system.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the structure of the liquid crystal display element manufactured by the Example and the comparative example.
2 is a schematic view showing an electrode structure of a liquid crystal display device manufactured in Examples and Comparative Examples.

(Mode for carrying out the invention)

Hereinafter, the form of the liquid crystal aligning agent of this invention and a liquid crystal display element is demonstrated in detail.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of this invention contains a compound [A] as a liquid crystal aligning agent for liquid crystal aligning film formation in the liquid crystal display element of IPS and FFS system. In addition, the said liquid crystal aligning agent can contain the "other polymer" mentioned later, such as a [B] polymer. In addition, the said liquid crystal aligning agent may contain other arbitrary components in the range which does not impair the effect of this invention. Each component will be described in detail below.

<[A] compound>

The compound (A) is a compound having a group represented by Formula (1). The group represented by said formula (1) has dielectric anisotropy, and the liquid crystal aligning agent containing the compound [A] is excellent in the orientation controllability of a liquid crystal molecule. For this reason, the liquid crystal display element of the IPS and FFS system provided with the liquid crystal aligning film formed using the said liquid crystal aligning agent has favorable orientation of liquid crystal molecules, and can shorten a response time.

In said formula (1), R <^1> is group which has at least two monocyclic structure, Preferably, it shows positive or negative dielectric anisotropy. A monocyclic structure is a structure which does not have what is called a condensed cyclic structure in which one ring structure exists independently from another ring structure, and the bond of one ring structure is shared with the other ring structure. In addition, as a monocyclic structure, any of an alicyclic structure, an aromatic ring structure, and a heterocyclic structure may be sufficient, and you may have it in combination.

R ¹ is not particularly limited as long as it is a group having at least two monocyclic structures. Typically, R ¹ is preferably a group represented by the formula (3). By introducing the structure represented by said formula (3) to the side chain of the [A] compound of the said liquid crystal aligning agent, the liquid crystal response speed of the liquid crystal aligning element obtained can be made further faster.

In said formula (3), R <^4> is any of a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, and an alkoxy group. As an alkoxycarbonyl group, For example, as an alkyl group, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, carbon number, such as a methyl group, an ethyl group, a propyl group, n-butyl group, an isobutyl group, is 1, for example. As an alkoxy group, such as a linear or branched alkyl group of -20, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example.

In Formula (3), when there are two or more R <^4> , you may use combining the different thing, respectively. As a combination in the case of having a plurality of R ⁴ , in order to stably express desired dielectric anisotropy, a combination of a fluorine atom and a cyano group, a combination of a fluorine atom and an alkyl group, and a combination of a cyano group and an alkyl group are preferable. In addition, b is an integer of 0-9.

In formula (3), R <^5> and R <^7> is respectively independently a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylene phenylene group, or a heterocyclic ring. As a heterocyclic ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, etc. are mentioned, for example.

In said Formula (3), R <^6> connects R <^5> and R <^7> containing any of a C1-C10 alkylene group, a double bond, a triple bond, an ether bond, an ester bond, and a heterocycle. It is a coupling group, and these groups (alkylene group and heterocycle) may further have a substituent. It can select suitably according to the orientation or induced anisotropy which a compound (A) requires. In addition, since c is an integer of 0 or 1, even if R <^6> is included, it is not necessary to include it.

In said formula (3), d is an integer of 1-2. When d is 2, some R <^6> and R <^7> may be same or different, respectively.

As group represented by said formula (3), group represented by following formula (D-1)-(D-116) is mentioned, for example.

In formulas (D-1) to (D-116), R represents an alkyl group having 1 to 20 carbon atoms (methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, etc.) Or an alkoxy group (methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, etc.).

In said formula (1), R <^2> is a coupling group containing any of a double bond, a triple bond, an ether bond, an ester bond, and an oxygen atom. R ² may include any of the above bonds, but may be included in combination of each bond. In addition, when R <^{3> mentioned} later is a phenylene group or a cyclohexylene group, it is preferable that R <^2> contains the C1-C30 alkylene group from a viewpoint of the orientation of the orientation film formed, or the solubility to a solvent. In addition, a is an integer of 0-1.

Although it does not specifically limit as a compound (A) as long as it has group represented by said Formula (1), The polymer which has group represented by Formula (1) in a side chain is preferable, A polyorganosiloxane, a polyimide, a polyamic acid, a polyacrylate is preferable. , Polymethacrylate, poly (styrene-phenylmaleimide) derivatives, cellulose derivatives, polyesters, polyamides, polystyrene derivatives, and polyamic acid esters are more preferable in terms of electrical properties, and in terms of light resistance. It is more preferable to make polyorganosiloxane the main chain structure.

As [A] compound which has a polyorganosiloxane as a main chain structure, it is preferable that it is a compound which has the part derived from the polyorganosiloxane which has an epoxy group, and the part derived from the specific carboxylic acid represented by said formula (2). When the [A] compound in the said liquid crystal aligning agent has a specific structural unit, the structure which has dielectric anisotropy in the side chain is introduce | transduced, and the liquid crystal display element provided with the liquid crystal aligning film formed using this liquid crystal aligning agent is more responsive. The time is shortened. Further, by utilizing the reactivity between the epoxy group and the carboxyl group, a structure having dielectric anisotropy represented by the formula (1) as the side chain in the polyorganosiloxane as the main chain can be easily introduced.

When the compound (A) has a moiety derived from a polyorganosiloxane having an epoxy group and a moiety derived from the specific carbonic acid, the compound (A) is mainly obtained as a reactant of an epoxy group of a polyorganosiloxane and a carboxyl group of a specific carbon acid. In order to facilitate the following description, the compound [A] will be described by dividing it into a part derived from a polyorganosiloxane (and its derivative) having an epoxy group and a part derived from a specific carboxylic acid for convenience.

[Part derived from polyorganosiloxane having an epoxy group]

This part is a concept including the polyorganosiloxane skeleton as a polymer main chain and the epoxy group containing skeleton as a side chain extended from this polyorganosiloxane main chain in the structure of the compound [A]. As described above, in the compound [A], most of the epoxy groups react with the specific carbonic acid and do not have the initial structure. However, the specific carbonic acid may be bonded to a portion other than the epoxy group. Therefore, in this invention, it is assumed that it is "a part derived from the polyorganosiloxane which has an epoxy group" including both aspects.

When the compound (A) has an epoxy group such as a group containing a glycidyl group, a glycidyloxy group, and an epoxycyclohexyl group, the liquid crystal aligning agent further improves electrical characteristics such as orientation and high-speed response. Is an epoxy group as the group represented by the formula (X ¹ -1) or (X ¹ -2) is preferred. By incorporating the group represented by the formula (X ¹ -1) or (X ¹ -2) into the polyorganosiloxane, introducing the group represented by the formula (1) to the side chain by using a specific carbonic acid in the compound [A] Easier

Group is represented by wherein the formula the formula (X ¹ -1) or (X ¹ -2) is preferred.

As for the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) of the polyorganosiloxane which has an epoxy group, 500-100,000 are preferable, 1,000-50,000 are more preferable, 1,000-20,000 are especially preferable Do.

[Synthesis method of polyorganosiloxane having an epoxy group]

The polyorganosiloxane having such an epoxy group preferably hydrolyzes a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound in the presence of a suitable organic solvent, water and a catalyst. Or it can synthesize | combine by hydrolysis and condensation.

As a silane compound which has the said epoxy group, 3-glycidyloxy propyl trimethoxysilane, 3-glycidyl oxypropyl triethoxy silane, 3-glycidyl oxypropyl methyl dimethoxy silane, 3-glycol, for example Cydyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyl Oxyethyltriethoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 2-glycidyloxyethyldimethylmethoxysilane, 2-glycidyloxyethyl Dimethylethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltriethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldie Methoxysilane, 4-glycidyloxybutyldimethylmethoxysilane, 4-glycidyloxybutyldimethylethoxy Column, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimeth And oxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, and the like. These may use individually or 2 or more types.

Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra- -Butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri- , Fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec -Methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltri- Tri-sec-butoxy silane, 2- (trifluoromethyl) ethyl trichlorosilane, 2- Rhomethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri -i-propoxysilane, 2- (trifluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n- Hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n- Hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-butoxysilane , 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyltri Methoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (Perfluoro-n-octyl) ethyl tri-n-octyl) ethyl tri-i-propoxysilane, 2- (perfluoro- Tri-sec-butoxysilane, hydroxymethyl trichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propyl (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, (Meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri- (Meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltriethoxysilane, Mercaptopropyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, N-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxy Silane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyl Triethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri- butoxysilane, methyldi-n-butoxysilane, methyldi-n-butoxysilane, methyldi-n-butoxysilane, methyldimethoxysilane, methyldiethoxysilane, butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-n-butoxy silane, dimethyl di-n-butoxy silane, dimethyldimethoxy silane, dimethyl diethoxy silane, dimethyl di- (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro- n-octyl) ethyl] dichlorosilane, (Methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (Methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (Perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (methyl) (3- mercaptopropyl) dichlorosilane, (methyl) (Methyl) (3-mercaptopropyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (Methyl) (vinyl) dichlorosilane, (methyl) (3-mercaptopropyl) di-n-butoxysilane, (methyl) (Methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) diethoxysilane, (methyl) (vinyl) di-n-propoxysilane, (Vinyl) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propyl Butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiethoxysilane, diphenyldiethoxysilane, N-propoxy silane, diphenyl di-i-propoxy silane, diphenyl di-n-butoxy silane, diphenyl Di-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxy Trimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, Silanes having one silicon atom such as (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane and (ethoxy) (methyl) diphenylsilane The compound can be mentioned.

As a commercially available product, for example,

KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22-176B, X- 22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40- 9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, Shin-Etsu Chemical Co., Ltd.);

Glass Resin (Showa Denko);

SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Torre Dow Corning);

FZ3711 and FZ3722 (above, Nippon Unicas Co., Ltd.);

DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS- 227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, Chisso Corporation);

Methyl silicate MS51, methyl silicate MS56 (above, Mitsubishi Kagaku Corporation);

Ethyl Silicate 28, Ethyl Silicate 40, Ethyl Silicate 48 (above, Colcot);

GR100, GR650, GR908, and GR950 (all trade names, manufactured by Showa Denko K.K.).

Among these other silane compounds, from the viewpoint of the orientation and storage stability of the resulting liquid crystal aligning agent, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltri Methoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltrier Preferred are methoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane Do.

The polyorganosiloxane having an epoxy group preferably used in the present invention, in order to introduce a side chain having dielectric anisotropy in a sufficient amount, the epoxy equivalent is preferably 100 to 10,000 g / mol, more preferably 150 to 1,000 g / mol It is preferable and it is especially preferable that it is 150-300 g / mol. Therefore, when synthesize | combining the precursor of the polyorganosiloxane which has an epoxy group, it is prepared by setting the use ratio of a silane compound and another silane compound so that the epoxy equivalent of the polyorganosiloxane which has an epoxy group obtained may become said range. It is preferable. When synthesize | combining the polyorganosiloxane which has an epoxy group used by this invention, it is more preferable to use only a silane compound and not to use another silane compound.

Examples of the organic solvent that can be used in the synthesis of the polyorganosiloxane having an epoxy group include a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, and an alcohol compound.

As said hydrocarbon, For example, toluene, xylene, etc .; As said ketone, For example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone etc .; Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; As the ether, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; Examples of the alcohols include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Of these, non-water-soluble ones are preferable. These organic solvents may be used alone or in combination of two or more thereof.

The amount of the organic solvent used is preferably 10 to 10,000 parts by mass, and more preferably 50 to 1,000 parts by mass with respect to 100 parts by mass of all the silane compounds. The amount of water used when producing the polyorganosiloxane having an epoxy group is preferably 0.5 to 100-fold mole, and more preferably 1 to 30-fold mole with respect to all the silane compounds.

As the catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound and the like can be used.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicyclo-undecene; Quaternary organic amines, such as tetramethylammonium hydroxide, etc. are mentioned, respectively. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine in consideration of the fact that the reaction proceeds slowly; Quaternary organic amines, such as tetramethylammonium hydroxide, are preferable.

As a catalyst in manufacturing the polyorganosiloxane which has an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, the desired polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without generating side reactions such as ring opening of an epoxy group, and thus the production stability is excellent. desirable. Moreover, since the liquid crystal aligning agent which contains the reaction material of the polyorganosiloxane which has the epoxy group synthesize | combined using the alkali metal compound or the organic base as a catalyst, and a specific carbonic acid is very excellent in storage stability, it is suitable. The reason for this is that, as pointed out in Chemical Reviews, Vol. 95, p1409 (1995), when an alkali metal compound or an organic base is used as a catalyst in hydrolysis and condensation reactions, random structures, ladder structures, or cage shapes It is inferred whether or not the structure is formed and a polyorganosiloxane having a low content of silanol groups is obtained. Since the content ratio of silanol groups is small, condensation reaction of silanol groups is suppressed, and when the said liquid crystal aligning agent contains the other polymer mentioned later, since condensation reaction of a silanol group and other polymers is suppressed, It is inferred that the result is excellent storage stability.

As the catalyst, an organic base is particularly preferable. Although the usage-amount of an organic base differs according to reaction conditions, such as a kind of organic base, temperature, etc., it should be set suitably, For example, Preferably it is 0.01-3 times mole with respect to all the silane compounds, More preferably, it is 0.05 It is -1 time molar.

The hydrolysis or hydrolytic condensation reaction in the production of a polyorganosiloxane having an epoxy group can be carried out by dissolving an epoxy group-containing silane compound and, if necessary, other silane compounds in an organic solvent, mixing the solution with an organic base and water For example, by heating with an oil bath or the like.

In the case of the hydrolysis-condensation reaction, the heating temperature of the oil bath is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. desirable. During the heating, the mixed solution may be stirred or refluxed.

It is preferable to wash | clean the organic solvent layer fractionated from the reaction liquid after completion | finish of reaction with water. At the time of this washing | cleaning, it is preferable at the point which a washing operation becomes easy by washing with water containing a small amount of salts, for example, about 0.2 mass% ammonium nitrate aqueous solution. The washing is carried out until the water layer after the washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain a polyorganosiloxane having a desired epoxy group Siloxane can be obtained.

In the present invention, a commercially available polyorganosiloxane having an epoxy group may be used. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (manufactured by Chisso Corporation).

The compound (A) is a part derived from a hydrolyzate produced by the hydrolysis of the polyorganosiloxane itself having an epoxy group, or a part derived from a hydrolysis condensation product of the polyorganosiloxanes having an epoxy group hydrolyzed and condensed. It may include. These hydrolyzate and hydrolysis-condensate which are the constituent materials of the said part can also be prepared similarly to the hydrolysis and condensation conditions of the polyorganosiloxane which has an epoxy group.

[Part derived from specific carbonic acid]

This part derived from the specific carboxylic acid represented by said Formula (2) is couple | bonded with the structure derived from the epoxy group extended mainly from the polyorganosiloxane main chain among the structures of the [A] compound contained in the said liquid crystal aligning agent, It corresponds to the side chain structure which makes the structure derived from the carboxyl group which exists as a viewpoint. However, in this invention, even if the specific carbonic acid is couple | bonded with parts other than an epoxy group, suppose that it is a "part derived from a specific carbonic acid."

In the formula (2), R ¹ and R ² are the same as R ¹ and R ² in the aforementioned formula (1).

R <^3> of said Formula (2) is a methylene group or a C2-C30 alkylene group, a phenylene group, or a cyclohexylene group, These may further have a substituent.

Examples of the alkylene group having 2 to 30 carbon atoms include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, and hexadec Silenyl group, octadecylene group, nonadecylene group, eicosylene group, henoxysilane group, docosylene group, tricosylene group, tetracosylene group, pentacosylene group, hexacosylene group, heptacosylene group, An octacosylene group, a nonacosylene group, a triaconthylene group, etc. are mentioned. Among them, in order to stably express liquid crystal alignment, a pentylene group, a hexylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, a hexadecylene group, an octadecylene group An alkylene group having 5 or more and 20 or less carbon atoms, such as nonadecylene group and eicosylene group, is preferable.

As a compound which has a carboxyl group represented by said formula (2), the compound represented by following formula (E-1)-(E-25) is mentioned, for example.

In formulas (E-1) to (E-25), R ¹ has the same meaning as in formula (2). m is an integer of 1-30.

[Synthesis method of specific carbonic acid]

The synthesis procedure of a specific carbonic acid is not specifically limited, It can carry out combining a conventionally well-known method. As a typical synthesis procedure, for example, (1) a compound having a phenol skeleton and a compound in which an alkyl chain portion of a higher fatty acid ester is substituted with halogen are reacted under basic conditions, and the hydroxyl group of the phenol skeleton is substituted with carbon substituted with halogen. A bond is formed, and then the ester is reduced to form a specific carboxylic acid. (2) A compound having a phenol skeleton and ethylene carbonate are reacted to produce a terminal alcohol compound, and the hydroxyl group and the halogenated benzenesulfonyl chloride are reacted. Activating and then reacting methyl benzoate containing a hydroxyl group to the activating portion to generate a bond of the hydroxyl group of the terminal alcohol compound with the hydroxyl group of the terminal alcohol compound together with the hydroxyl group of the methyl benzoate containing a hydroxyl group as a substituent, followed by esterification. The method of reducing | reducing to specific carbonic acid etc. is illustrated. However, the synthesis order of specific carbonic acid is not limited to these.

<Synthesis method of compound [A]>

The method for synthesizing the compound [A] is not particularly limited and can be synthesized by a general known method. When the compound (A) has a part derived from a polyorganosiloxane having an epoxy group and a part derived from a specific carbon acid, the polyorganosiloxane having an epoxy group and the specific carbon acid are preferably present in the presence of a catalyst. It can synthesize | combine by making it react.

The specific carbon acid is preferably 0.001 to 10 mol, more preferably 0.01 to 5 mol, still more preferably 0.05 to 2 mol with respect to 1 mol of the epoxy group of the polyorganosiloxane.

In this invention, you may replace and use a part of specific carboxylic acid with the compound represented by following formula (4) in the range which does not impair the effect of this invention. In this case, the synthesis | combination of the compound [A] is performed by making the mixture of the polyorganosiloxane which has an epoxy group, specific carbonic acid, and the compound represented by following formula (4) react.

In said formula (4),

A <^1> is a C3-C10 cycloalkyl group which may be substituted by a C1-C30 linear or branched alkyl group, a C1-C20 alkyl group, or an alkoxyl group. However, one part or all part of the hydrogen atom of the said alkyl group and the alkoxy group may be substituted by substituents, such as a cyano group, a fluorine atom, and a trifluoromethyl group.

L ⁰ is a single bond, * -O-, * -COO- or * -OCO-. A bonding hand with "*" is bonded to A ¹ .

L ¹ is a single bond, an alkylene group having 1 to 20 carbon atoms, a phenylene group, a biphenylene group, a cyclohexylene group, a bicyclohexylene group, or a group represented by the following formula (L ¹ -1) or (L ¹ -2): to be.

Z is a monovalent organic group that can react with an epoxy group in the [A] polyorganosiloxane compound to form a bonding group.

However, when L ¹ is a single bond, L ⁰ is a single bond.

In the formulas (L ¹ -1) and (L ¹ -2), the bonding hand with "*" is bonded to Z, respectively.

Z is preferably a carboxyl group.

As a C1-C30 linear or branched alkyl group which A <^1> represents in said Formula (4), for example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group , tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3- Methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1, 2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, n-heptyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group , 1-methylhexyl group, 4,4-dimethylpentyl group, 3,4-dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,3 -Dimethylpentyl group, 1,3-dimethylpentyl group, 2,2-dimethylpentyl group, 1,2-dimethylpentyl group, 1,1-dimethylpentyl group, 2,3,3-trimethylbutyl group, 1,3 , 3-trimethylbutyl group, 1,2,3-t Methylbutyl group, n-octyl group, 6-methylheptyl group, 5-methylheptyl group, 4-methylheptyl group, 3-methylheptyl group, 2-methylheptyl group, 1-methylheptyl group, 2-ethylhexyl group , n-nonanyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n- tetradecyl group, n-heptadecyl group, n-hexadecyl group, n-heptadecyl group , n-octadecyl group, n-nonadecyl group and the like.

As a C3-C10 cycloalkyl group which may be substituted by the C1-C20 alkyl group or the alkoxy group, For example, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononanyl group, cyclodecyl group, cyclo Dodecyl group etc. are mentioned.

As A <^1> in said Formula (4), the group chosen from a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, and said Formula (A-1) or (A-3) is preferable.

As a compound represented by said formula (4), the compound represented by either of following formula (4-1)-(4-5) is preferable.

U is an integer of 1-5 in said Formula (4-1)-(4-5). v is an integer of 1-18. w is an integer of 1-20. k is an integer of 1-5. p is 0 or 1; q is an integer of 0-18. r is an integer of 0-18. s and t are the integers of 0-2 each independently.

Among these compounds, compounds represented by the following formulas (4-6) to (4-11) are more preferable.

In this specification, the compound represented by said Formula (4) may be called "other carboxylic acid compound" hereafter.

In the present invention, in the case where other carbonic acid compounds are used together with the specific carbonic acid, the use ratio of the sum of the specific carbonic acid and other carbonic acid compounds is preferably 0.001 to 1.5 with respect to 1 mol of the epoxy group of the polyorganosiloxane. Mol, More preferably, it is 0.01-1 mol, More preferably, it is 0.05-0.9 mol. In this case, the other carbonic acid compound is preferably used in a range of 40 mol% or less, more preferably 20 mol% or less, based on the total amount with the specific carbon acid. When the use ratio of other pretilt-angle expressing compound exceeds 40%, a bad influence may appear in the viewing angle characteristic of a liquid crystal display element.

As a catalyst used for reaction of the epoxy group in a polyorganosiloxane with another carbonic acid compound, a well-known compound can be used as an organic base or what is called a hardening accelerator which promotes reaction of an epoxy compound and an acid anhydride.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicyclo-undecene; And quaternary organic amines such as tetramethylammonium hydroxide. Among these organic bases, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and tetramethylammonium hydroxide are preferable.

As the curing accelerator, for example,

Tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine and triethanolamine;

2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methyldi Midazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl)- 2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, 1- (2- Cyanoethyl) -2-phenyl-4,5-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimelli Tate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4- Diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s Triazine, 2,4-di Mino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, 2-phenylimidazole Imidazole compounds such as isocyanuric acid adducts and isocyanuric acid adducts of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine;

Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenphosphate; Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide Nium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium O, O-diethylphosphorodithioate, tetra-n-butylphosphonium benzotriazoleate, tetra-n-butylphosphonium tetra Quaternary phosphonium salts such as fluoroborate, tetra-n-butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;

Organometallic compounds such as zinc octylate, tin octylate and aluminum acetyl acetone complex;

Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride;

Boron compounds such as boron trichloride and triphenyl borate;

Metal halide compounds such as zinc chloride and stannic chloride;

A high melting point dispersed latent curing accelerator such as an amine addition type accelerator such as dicyandiamide or an adduct of an amine with an epoxy resin;

A microcapsulated latent curing accelerator in which the surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer;

Amine salt type latent curing accelerator;

And latent curing accelerators such as high-temperature dissociation-type thermal cationic polymerization-type latent curing accelerators such as Lewis salts and Bronsted salts.

Among these catalysts, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride are preferable.

The catalyst is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, still more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyorganosiloxane having an epoxy group.

Reaction temperature becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 50-150 degreeC. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

The synthesis reaction of the compound (A) can be carried out in the presence of an organic solvent as necessary. As such an organic solvent, a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, an alcohol compound etc. are mentioned, for example. Of these, ether compounds, ester compounds, and ketone compounds are preferable from the viewpoints of solubility of raw materials and products and ease of purification of products. As for a solvent, solid content concentration (the ratio which the mass of components other than the solvent in a reaction solution occupies for the total mass of a solution) becomes like this. Preferably it is 0.1 mass% or more and 70 mass% or less, More preferably, it is 5 mass% or more and 50 mass% or less Is used in the amount

Although the weight average molecular weight in styrene conversion by the gel permeation chromatography of the compound [A] obtained in this way is not specifically limited, It is preferable that it is 1,000-200,000, and it is more preferable that it is 2,000-20,000. Within this molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

The said compound (A) introduce | transduces the structure derived from specific carbonic acid to the polyorganosiloxane which has an epoxy group by ring-opening addition to the epoxy group of the carboxylate part of specific carbonic acid. This manufacturing method is easy and is a very suitable method in that the introduction ratio of the structure derived from a specific carbonic acid can be made high.

<Optional ingredients>

In addition to the said [A] compound, the said liquid crystal aligning agent is a polymer other than the [A] compound (henceforth a "other polymer" may be called), a hardening | curing agent, for example, unless the effect of this invention is impaired, Other optional components such as a curing catalyst, a curing accelerator, a compound having at least one epoxy group in the molecule (hereinafter may be referred to as an "epoxy compound"), a functional silane compound, and a surfactant may be contained.

[Other Polymers]

The other polymer can be used in order to improve the solution characteristic of the said liquid crystal aligning agent, and the electrical characteristic of the obtained liquid crystal display element further. As other polymers, for example

At least one polymer ([B] polymer) selected from the group consisting of polyamic acid and polyimide;

At least one selected from the group consisting of a polyorganosiloxane represented by the following formula (5), a hydrolyzate thereof and a condensate of the hydrolyzate thereof (hereinafter, may be referred to as "other polyorganosiloxane");

Polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like.

In formula (5), X <^1> is a hydroxyl group, a halogen atom, a C1-C20 alkyl group, a C1-C6 alkoxy group, or a C6-C20 aryl group. Y ¹ is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

<[B] polymer>

The polymer (B) is at least one polymer selected from the group consisting of polyamic acid and polyimide. Hereinafter, polyamic acid and polyimide are explained in full detail.

[Polyamic acid]

The polyamic acid is obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound. As tetracarboxylic dianhydride which can be used for the synthesis | combination of a polyamic acid, For example, 2,3,5- tricarboxy cyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride, 1,2,3,4- cyclobutane tetra Carboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 3,5,6-tree Carboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2 , 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro -2,5-dioxo-3-furanyl) -8-methyl-naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) 3-Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo [2.2.2] -octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, formula (F Tet represented by -1) to (F-14) Carboxylic acid dianhydride such as the aliphatic or alicyclic tetracarboxylic acid dianhydride;

Pyromellitic dianhydride, 3,3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetra Carboxylic acid dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3,3 ', 4 , 4'-tetraphenylsilanetetracarboxylic acid dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride , 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride, p-phenylene Bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (tripe Acid), and aromatic tetracarboxylic acid dianhydride, such as 4,4'-diphenylmethane dianhydride.

Among them, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1 , 3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -8-methyl-naphtho [1,2- c] -furan-1,3-dione, 2,3,5-tricarboxycyclopentylacetic dianhydride, butanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarbon Acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5 Tetracarboxylic dianhydride represented by, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride This is preferred. These tetracarboxylic dianhydrides may be used alone or in combination of two or more thereof.

As a diamine compound which can be used for the synthesis | combination of a polyamic acid, it is o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'-dia, for example. Minodiphenylsulphide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl ) Biphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4 -Aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'- (p-phenylenediisopropylidene) bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis ( 4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocar bar Sol, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis (4- Aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid , Dodecaneoxy-2,4-diaminobenzene, tetradecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octa Decanoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy -2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyl Oxy-2,4-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-di Aminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclo Hexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl ) Phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) Phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N- Diallyl aniline, 4-aminobenzylamine, 3-aminobenzylamine, 1- (2,4-diaminophenyl) piperazin-4-carboxylic acid, 4- (morpholin-4-yl) benzene-1,3 -Diamine, 1,3-bis (N- (4-aminophenyl) piperidinyl) propane, α-amino-ω-aminophenylalkylene, 4-aminophenyl-4-aminobenzoate, 4,4'- [4,4'- Ropan-1,3-diyl bis (piperidine-1,4-diyl) dianiline, diethylene glycol (di-4-aminophenyl) ether,

Aromatic diamines having a hetero atom such as diaminotetraphenylthiophene;

Metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4- Diaminocyclohexane, cyclohexanebis (methylamine), isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] Aliphatic or alicyclic diamines such as undecylenedimethyldiamine and 4,4'-methylenebis (cyclohexylamine);

And diaminoorganosiloxanes such as diaminohexamethyldisiloxane and the like.

Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-2,2'-dimethylbiphenyl, cyclohexanebis (methylamine), 1,5-dia Minonaphthalene, 2,7-diaminofluorene, 4,4'-diaminodiphenylether, 4,4 '-(p-phenyleneisopropylidene) bisaniline, 2,2-bis [4- (4 -Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) Phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy C] -octafluorobiphenyl, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4-dia Minobenzene, 1-cholestanyloxy-2,4-diaminobenzene, hexadecyloxy (3,5-diaminobenzoyl), octadecyloxy (3,5-diaminobenzoyl), cholesteryloxy (3,5-di Minobenzoyl), cholestanyloxy (3,5-diaminobenzoyl), 4-aminophenyl-4-aminobenzoate, 4,4 '-[4,4'-propane-1,3-diylbis (pi Preference is given to diamines represented by ferridine-1,4-diyl)] dianiline and diethylene glycol (di-4-aminophenyl) ether. These diamines may be used alone or in combination of two or more.

The use ratio of the tetracarboxylic dianhydride and the diamine compound provided in the polyamic acid synthesis reaction is preferably a ratio in which the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group contained in the diamine compound. More preferably, it is a ratio which becomes 0.3-1.2 equivalent.

Synthesis reaction of polyamic acid, Preferably in an organic solvent, Preferably it is -20-150 degreeC, More preferably, on the temperature conditions of 0-100 degreeC, Preferably it is 0.5 to 24 hours, More preferably, It is performed for 2 to 10 hours. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide Aprotic polar solvents such as N, N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; phenol-based solvents such as m-cresol, xylenol, phenol, and halogenated phenol. As for the usage-amount (a) of an organic solvent, the total amount (b) of tetracarboxylic dianhydride and a diamine compound is 0.1-50 mass% with respect to the total amount (a + b) of a reaction solution, More preferably, it is 5-30 It is an amount as it becomes mass%.

In the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of polyamic acid, can be used together in a range in which the resulting polyamic acid does not precipitate. As such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, ethylene glycol monomethyl ether, ethyl lactate Butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, propylene carbonate, diethyl oxalate, Diethyl lonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether To ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl Le, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4- Dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like. These poor solvents may be used alone or in combination of two or more thereof.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent, or after the isolated polyamic acid is purified, . Isolation of polyamic acid can be performed by pouring the said reaction solution in a large quantity of poor solvents, obtaining a precipitate, and drying this precipitate under reduced pressure, or distilling off a reaction solution by the evaporator under reduced pressure. Moreover, polyamic acid can be refine | purified by the method of melt | dissolving this polyamic acid again in an organic solvent, and then precipitating with a poor solvent, or performing the process of distilling under reduced pressure with an evaporator once or several times. .

[Polyimide]

The said polyimide can be manufactured by dehydrating and ring-closing the dark acid structure which the polyamic acid obtained as mentioned above has. At this time, all of the dark acid structures may be dehydrated and completely imidized, or only a part of the dark acid structures may be dehydrated and closed to be a partial imide in which the dark acid structure and the imide structure coexist.

The dehydration ring closure of polyamic acid may be carried out by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating it as necessary. Is done by.

The reaction temperature in the method of heating the polyamic acid of said (i) becomes like this. Preferably it is 50-200 degreeC, More preferably, it is 60-170 degreeC. By making reaction temperature into 50 degreeC or more, dehydration ring-closure reaction can fully advance and the fall of the molecular weight of the imidation polymer obtained can be suppressed by making reaction temperature into 200 degrees C or less. The reaction time in the method of heating a polyamic acid becomes like this. Preferably it is 0.5 to 48 hours, More preferably, it is 2 to 20 hours.

On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of the polyamic acid of said (ii), acid anhydrides, such as acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used as a dehydrating agent, for example. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of polyamic acid structural units. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. However, the present invention is not limited thereto. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C, and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

In the method (ii), a reaction solution containing a polyimide is obtained as described above. This reaction solution may be provided as it is in the preparation of a liquid crystal aligning agent or may be provided in the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. Alternatively, after the polyimide is isolated, Or may be provided to the preparation of a liquid crystal aligning agent after purification of the isolated polyimide. In order to remove a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, methods, such as solvent substitution, can be applied, for example. Isolation and purification of a polyimide can be performed by performing the same operation as the above as an isolation | purification and purification method of polyamic acid.

[Other polyorganosiloxane]

The said liquid crystal aligning agent may contain other polyorganosiloxane besides the [A] compound containing the part derived from polyorganosiloxane. It is preferable that the other polyorganosiloxane is at least 1 sort (s) chosen from the group which consists of a polyorganosiloxane represented by said formula (5), its hydrolyzate, and the condensate of this hydrolyzate. In addition, when the said liquid crystal aligning agent contains other polyorganosiloxane, most of other polyorganosiloxane exists independently of the [A] compound, and part thereof as a condensate with the [A] compound. May exist.

In X ¹ and Y ¹ in the formula (5),

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octade Practical groups, n-nonadecyl groups, n-eicosyl groups and the like;

As a C1-C16 alkoxy group, For example, a methoxy group, an ethoxy group, etc .;

As the aryl group having 6 to 20 carbon atoms, for example, a phenyl group and the like can be given.

The other polyorganosiloxane is preferably at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter sometimes referred to as "raw material silane compound"). In a solvent, it can synthesize | combine by hydrolysis or hydrolysis-condensation in presence of water and a catalyst.

As a raw silane compound which can be used here, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec -Butoxysilane, tetra-tert-butoxysilane, tetrachlorosilane; Methyltrimethoxysilane, Methyltriethoxysilane, Methyltri-n-propoxysilane, Methyltri-iso-propoxysilane, Methyltri-n-butoxysilane, Methyltri-sec-butoxysilane, Methyltri -tert-butoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyl tree -n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane; Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane; Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, etc. are mentioned. Among these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and trimethylmethoxy Silane and trimethylethoxysilane are preferable.

When synthesize | combining other polyorganosiloxane, as an organic solvent which can be arbitrarily used, an alcohol compound, a ketone compound, an amide compound, or an ester compound, or other aprotic compound is mentioned, for example. These may use individually or 2 or more types.

As the alcohol compound, for example,

Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t- Pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol , sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec- tetradecyl alcohol, sec-heptadecyl alcohol, phenol Monoalcohol compounds such as cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol;

Propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4- Polyhydric alcohol compounds such as 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl ether, 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 And partial ethers of polyhydric alcohol compounds such as glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether. These alcohol compounds may be used alone or in combination of two or more.

As a ketone compound, for example

Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl Monoketone compounds such as ketones, di-i-butyl ketones, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fencone;

Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonane Dione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetra methyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4 (Beta) -diketone compounds, such as -heptanedione, etc. are mentioned. These ketone compounds may be used alone or in combination of two or more thereof.

As said amide compound, for example, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N , N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N -Formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. These amide compounds may be used alone or in combination of two or more.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate and acetic acid. n-butyl, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, Cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetic acid, ethyl acetoacetic acid, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate Ether, diethylene glycol mono-n-butyl ether, acetic acid propylene glycol mono Butyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, Ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl lactate, dimethyl phthalate, diphthalate Ethyl and the like. These ester compounds may be used alone or in combination of two or more.

As other aprotic compounds, for example, acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethyl phosphate triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-pi Peridone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone Etc. can be mentioned. Among these solvents, polyhydric alcohol compounds, partial ethers of polyhydric alcohol compounds, or ester compounds are particularly preferred.

The amount of water used in the synthesis of other polyorganosiloxanes is preferably 0.01 to 100 moles, more preferably 0.1 to 30 moles based on 1 mole of the total amount of the alkoxy group and the halogen atom of the raw silane compound. Mole, and further preferably 1 to 1.5 moles.

As a catalyst which can be used at the time of the synthesis | combination of other polyorganosiloxane, a metal chelate compound, an organic acid, an inorganic acid, an organic base, ammonia, an alkali metal compound, etc. are mentioned, for example.

Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, and tri-i-propoxy mono (acetylacetonate) titanium. , Tri-n-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy bis (Acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, di-n-butoxy bis (acetylacetonate) Titanium, di-sec-butoxy bis (acetylacetonate) titanium, di-t-butoxy bis (acetylacetonate) titanium, monoethoxy tris (acetylacetonate) titanium, mono-n-propoxy Tris (acetylacetonate) titanium, mono-i-propoxy tris (acetylacetonate) Titanium, mono-n-butoxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (Acetylacetonate) titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) titanium, tri -n-butoxy mono (ethylacetoacetate) titanium, tri-sec-butoxy mono (ethylacetoacetate) titanium, tri-t-butoxy mono (ethylacetoacetate) titanium, diethoxy bis (ethyl Acetoacetate) titanium, di-n-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-n-butoxy bis (ethylacetoacetate) titanium, Di-sec-butoxy bis (ethylacetoacetate) titanium, di-t-butoxy Bis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate) titanium, mono-i-propoxy tris (ethylacetoacetate) titanium, Mono-n-butoxy tris (ethylacetoacetate) titanium, mono-sec-butoxy tris (ethylacetoacetate) titanium, mono-t-butoxy tris (ethylacetoacetate) titanium, tetrakis (ethylaceto Titanium chelate compounds, such as acetate) titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium ;

Triethoxy mono (acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) zirconium, tri-i-propoxy 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, di-i-propoxy bis (acetylacetonate) zirconium, di-n-butoxy bis (acetylacetonate) zirconium, di-sec-butoxy Bis (acetylacetonate) zirconium, di-t-butoxy bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris (acetylacetonate) zirconium, Mono-i-propoxy tris Cetylacetonate) zirconium, mono-n-butoxy tris (acetylacetonate) zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium , Tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i-propoxy 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, di-i-propoxy bis (ethylacetoacetate) zirconium, di-n-butoxy bis (ethylace Acetate) zirconium, di-sec-butoxybis (ethylacetoacetate) zirconium, di-t-butoxybis (ethylacetoacetate) zirconium, monoethoxytris (ethylacetoacetate) zirconium, mono-n- Propoxy tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate) zirconium, mono-n-butoxy tris (ethylacetoacetate) zirconium, mono-sec-butoxy tris ( Ethylacetoacetate) zirconium, mono-t-butoxytris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) Zirconium chelate compounds such as bis (ethylacetoacetate) zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium;

And aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum.

Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanic 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, melit acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloro Acetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.

As said inorganic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, etc. are mentioned, for example.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine and monomethyl diethanol. Amine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydrooxide, etc. are mentioned.

As said alkali metal compound, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide etc. are mentioned, for example. These catalysts may be used alone or in combination of two or more.

Of these catalysts, metal chelate compounds, organic acids and inorganic acids are preferred. As a metal chelate compound, a titanium chelate compound is more preferable.

The usage-amount of a catalyst becomes like this. Preferably it is 0.001-10 mass parts with respect to 100 mass parts of raw material silane compounds, More preferably, it is 0.001-1 mass part.

The catalyst may be added in advance in the silane compound as the raw material or in a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in the added water.

Water added during the synthesis of other polyorganosiloxanes can be added intermittently or continuously in a silane compound as a raw material or in a solution in which the silane compound is dissolved in an organic solvent.

As reaction temperature at the time of the synthesis | combination of other polyorganosiloxane, Preferably it is 0-100 degreeC, More preferably, it is 15-80 degreeC. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

When the said liquid crystal aligning agent contains another polymer with the [A] compound, as content of another polymer, it is preferable that it is 10,000 mass parts or less with respect to 100 mass parts of [A] compounds. More preferable content of another polymer changes with kinds of other polymers.

As a preferable use ratio of both when the said liquid crystal aligning agent contains a [A] compound and a [B] polymer, 100-5,000 mass parts of total amounts of a [B] polymer are preferable with respect to 100 mass parts of [A] compounds. , 200-3,000 mass parts is more preferable.

In addition, when the said liquid crystal aligning agent contains a [A] compound and other polyorganosiloxane, the preferable use ratio of both is as quantity of the other polyorganosiloxane with respect to 100 mass parts of [A] compounds. It is 100-2,000 mass parts.

When the said liquid crystal aligning agent contains another polymer with the compound [A], as another polymer, [B] polymer or other polyorganosiloxane is preferable.

[Curing agent, curing catalyst and curing accelerator]

A hardening | curing agent and a hardening catalyst can be contained in the said liquid crystal aligning agent for the purpose of strengthening the crosslinking reaction of the [A] compound. A hardening accelerator can be included in the said liquid crystal aligning agent for the purpose of promoting the hardening reaction which a hardening | curing agent plays.

As a hardening | curing agent, the hardening | curing agent generally used for hardening of the curable compound containing an epoxy group or the compound which has an epoxy group can be used. As such a hardening | curing agent, polyhydric amine, polyhydric carboxylic acid anhydride, polyhydric carboxylic acid is mentioned, for example.

As polyhydric carboxylic anhydride, the anhydride of cyclohexane tricarboxylic acid and other polyhydric carboxylic acid anhydride are mentioned, for example.

As cyclohexane tricarboxylic acid anhydride, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4- anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5- anhydride, cyclo Hexane-1,2,3-tricarboxylic acid-2,3-acid anhydride and the like. As other polyhydric carboxylic acid anhydride, for example, 4-methyltetrahydrophthalic anhydride, methylnadic acid anhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, following formula (6) Diels-Alder reaction products of alicyclic compounds having conjugated double bonds such as α-terpinene and allocymen and maleic anhydride, in addition to tetracarboxylic dianhydrides generally used for the synthesis of compounds and polyamic acids to be represented, and these Hydrogenated substance etc. are mentioned.

In formula (6), x is an integer of 1-20.

As the curing catalyst, for example, an antimony hexafluoride compound, a phosphorus hexafluoride compound, an aluminum trisacetylacetonate, or the like can be used. These catalysts can catalyze the cationic polymerization of an epoxy group by heating.

As the curing accelerator, for example, an imidazole compound; A quaternary compound; Quaternary amine compounds; Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; Organometallic compounds such as zinc octylate, tin octylate and aluminum acetyl acetone complex; Boron compounds such as boron trichloride and triphenyl borate; Metal halide compounds such as zinc chloride and stannic chloride; A high melting point dispersing latent curing accelerator such as dicyandiamide, an amine addition type accelerator such as an adduct of an amine and an epoxy resin; A microcapsulated latent curing accelerator in which a surface of a quaternary phosphonium salt or the like is coated with a polymer; Amine salt type latent curing accelerator; High temperature dissociation type | mold thermal cationic polymerization type latent hardening accelerator, such as a Lewis acid salt and Bronsted acid salt, etc. are mentioned.

[Epoxy Compound]

The said epoxy compound can be contained in the said liquid crystal aligning agent from a viewpoint of improving the adhesiveness with respect to the board | substrate surface of the liquid crystal aligning film formed.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol di. Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6- tetraglycol Cydyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane , N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N, -diglycidyl-benzylamine, N, N-diglycidyl-amino Methylcyclohexane is preferred.

When the said liquid crystal aligning agent contains an epoxy compound, Preferably it is 0.01-40 mass parts with respect to a total of 100 mass parts of said [A] polyorganosiloxane compound and the other polymer arbitrarily used. Hereinafter, More preferably, it is 0.1-30 mass parts.

Moreover, when the said liquid crystal aligning agent contains an epoxy compound, you may use together base catalysts, such as 1-benzyl- 2-methylimidazole, in order to raise the crosslinking reaction efficiently.

[Functional silane compound]

A functional silane compound can be used for the purpose of improving the adhesiveness with the board | substrate of the liquid crystal aligning film obtained. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane , N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silane triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl- 6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N- Bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. The reactant of the tetracarboxylic dianhydride described in Unexamined-Japanese-Patent No. 63-291922 with the silane compound which has an amino group, etc. are mentioned.

When the said liquid crystal aligning agent contains a functional silane compound, as the content ratio, 50 mass parts or less are preferable with respect to a total of 100 mass parts of the said [A] polymer and the other polymer used arbitrarily, and 20 mass parts The following is more preferable.

[Surfactants]

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, fluorine-containing surfactants, and the like.

When the said liquid crystal aligning agent contains surfactant, it is 10 mass parts or less with respect to all 100 mass parts of liquid crystal aligning agents as the content rate, More preferably, it is 1 mass part or less.

<Preparation method of liquid crystal aligning agent>

As mentioned above, although the said liquid crystal aligning agent contains a [A] polymer as an essential component and may contain other arbitrary components as needed, Preferably the composition of the solution state in which each component melt | dissolved in the organic solvent is preferable. As prepared.

As an organic solvent which can be used in order to prepare the said liquid crystal aligning agent, it is preferable to melt | dissolve [A] compound and other components used arbitrarily, and to not react with these. The organic solvent which can be used suitably for the said liquid crystal aligning agent changes with kinds of other polymer added arbitrarily.

As a preferable organic solvent in the case where the said liquid crystal aligning agent contains a [A] compound and a [B] polymer, the organic solvent illustrated above as what is used for synthesis | combination of a polyamic acid is mentioned. Under the present circumstances, you may use together the poor solvent illustrated as what is used for the synthesis | combination of the polyamic acid of this invention. These organic solvents may be used alone or in combination of two or more thereof.

On the other hand, when the said liquid crystal aligning agent contains only [A] compound as a polymer, or when it contains [A] compound and other polyorganosiloxane, it is 1-ethoxy-2, for example. Propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve Acetate, ethyl cellosolve acetate, propyl cellosol Acetate, butyl cellosolve acetate, methylcarbitol, ethylcarbitol, propylcarbitol, butylcarbitol, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, N-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate And isoamyl acetate. Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate and sec-pentyl acetate are preferable.

The preferable solvent used for preparation of the said liquid crystal aligning agent can be obtained combining the 1 or more types of said organic solvent according to the presence or absence of use of the other polymer, and its kind. In such a solvent, each component contained in a liquid crystal aligning agent does not precipitate in the following preferable solid content concentration, and the surface tension of a liquid crystal aligning agent becomes a range of 25-40 mN / m.

Although the ratio of solid content concentration of the said liquid crystal aligning agent, ie, the mass of all components other than the solvent in a liquid crystal aligning agent, to the total mass of a liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., Preferably it is 1-10 mass% Range. Although the said liquid crystal aligning agent is apply | coated to the surface of a board | substrate, and forms the coating film used as a liquid crystal aligning film, when solid content concentration is 1 mass% or more, the film thickness of this coating film becomes hard to become small and a favorable liquid crystal aligning film can be obtained. On the other hand, when solid content concentration is 10 mass% or less, it can suppress that the film thickness of a coating film becomes excessive and can obtain a favorable liquid crystal aligning film, and also prevents the viscosity of a liquid crystal aligning agent from increasing, and makes coating property favorable. Can be. A particularly preferable range of the solid concentration is different depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, when using the spinner method, the range of 1.5-4.5 mass% is especially preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by mass, and the solution viscosity is in the range of 12 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1-5 mass%, and to make solution viscosity into the range of 3-15 mPa * s. The temperature at the time of preparing the said liquid crystal aligning agent becomes like this. Preferably it is 0 degreeC-200 degreeC, More preferably, it is 0 degreeC-40 degreeC.

<Liquid crystal display element>

The liquid crystal display element of this invention is a liquid crystal display element of the IPS and FFS system provided with the liquid crystal aligning film formed from the said liquid crystal aligning agent. According to the said liquid crystal display element, when a liquid crystal aligning film is formed with the said liquid crystal aligning agent, liquid crystal aligning property and voltage holding ratio are high, and the outstanding high-speed response can be exhibited. Hereinafter, embodiment of a liquid crystal display element is described.

While the manufacturing method of the liquid crystal display element of this invention is demonstrated below, the manufacturing method of the liquid crystal aligning film of this invention is demonstrated also in the description. The liquid crystal display element of this invention can be manufactured by the process of the following (1)-(3), for example.

[Process (1): Formation of coating film]

First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, and then a coating film is formed on a board | substrate by heating a coating surface. The liquid crystal aligning agent of this invention is apply | coated respectively to one surface of the board | substrate with which the electrode pair patterned in the comb-shape, or the board | substrate with which the insulating layer was provided between the electrode pair, and the opposing board | substrate with which the electrode pair is not provided, respectively, and then each application surface The coating film is formed by heating. The liquid crystal aligning agent of this invention is apply | coated preferably by the offset printing method, the spin coating method, the roll coater method, or the inkjet printing method, respectively, and then each coating surface is heated (preferably preheating (prebaking) and baking ( 2 step heating) which consists of post-baking), and forms a coating film. Here, as a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. Examples of the transparent conductive film provided on one surface of the substrate include an NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), chromium, and the like. In order to obtain a patterned electrode, for example, by forming a patternless electrode film and then forming a pattern by photo etching, a method using a mask having a desired pattern when forming the electrode film, etc. Can be. At the time of application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface and an electrode film, and a coating film more favorable, a functional silane compound, a functional titanium compound, etc. are previously made to the surface which should form a coating film in the board | substrate surface. The pretreatment to apply may be performed.

A coating film is formed by preheating (prebaking) and then baking (postbaking) the coating surface after liquid crystal aligning agent application | coating. Prebaking conditions are 0.1 to 5 minutes, for example at 40-120 degreeC, and postbaking conditions are preferably 120-300 degreeC, More preferably, it is 150-250 degreeC, Preferably it is 5-200 minutes, More Preferably it is 10-100 minutes. After apply | coating a liquid crystal aligning agent on a board | substrate, the coating film used as an oriented film is formed by removing an organic solvent. At this time, when the polymer contained in the liquid crystal aligning agent of this invention is a polyamic acid or the imidized polymer which has an imide ring structure and a dark acid structure, it heats further after coating film formation, and advances dehydration ring-closure reaction, and is already It is good also as a drawing coating film. The film thickness of the coating film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

[Process (2): rubbing treatment]

When manufacturing a liquid crystal display element, the rubbing process which rubs a coating film formed as mentioned above with the roll which rolled cloth which consists of fibers, such as nylon, a rayon, a cotton, for example in a fixed direction is performed. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film.

[Process (3): Construction of liquid crystal cell]

With respect to the pair of substrates in which the liquid crystal alignment films are formed as described above, the two substrates are disposed to face each other so that the rubbing direction of the liquid crystal alignment films is reverse parallel. The peripheral part is bonded using a sealing agent, the liquid crystal is injected and filled into the cell surface partitioned by the substrate surface and the sealing agent, and the injection hole is sealed to form a liquid crystal cell. A liquid crystal display element can be obtained by joining a polarizing plate on the outer surface of the liquid crystal cell so that the polarizing direction thereof coincides with or orthogonal to the rubbing direction of the liquid crystal alignment film formed on each substrate.

As the sealing agent, for example, an epoxy resin containing a curing agent and an aluminum oxide spheres as a spacer can be used.

Examples of the liquid crystals include nematic liquid crystals and smectic liquid crystals, and among them, nematic liquid crystals are preferable, and for example, a sieve base liquid crystal, a subfamily clock liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal and an ester liquid crystal , Terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cuban-based liquid crystals, and the like. Furthermore, for these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonaate and cholesteryl carbonate; Chiral agents such as those sold under the trade names "C-15" and "CB-15" (Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, and the like may be added and used.

As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polarizing film called an "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched polyvinyl alcohol is sandwiched by a cellulose acetate protective film or a polarizing plate comprising a H film itself have.

[Example]

Hereinafter, although a synthesis example and an Example demonstrate this invention further in detail, this invention is not limited to these Examples.

The weight average molecular weight (Mw) of the polyorganosiloxane which has the epoxy group obtained in the following example, and the compound [A] is polystyrene conversion value measured by GPC of the following specification.

Column: Tososa, TSKgel GRCXLⅡ

Solvent: tetrahydrofuran

Temperature: 40 ℃

Pressure: 68kgf / ㎠

The necessary amounts of the starting compounds and polymers used in the following examples were ensured by repeating the synthesis of the starting compounds and the polymers in the synthesis scale shown in the following synthesis examples as necessary.

The viscosity of the polyamic acid obtained in the following example and the imidation ratio of polyimide are measured as follows.

[Solution viscosity of polymer solution]

The solution viscosity (mPa * s) of the polymer solution was measured at 25 degreeC using the E-type rotational viscometer about the solution adjusted to 10 mass% of polymer concentration using the predetermined solvent.

[Imidization Rate of Polyimide]

The polyimide solution was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference material. From the obtained ¹ H-NMR spectrum, the imidization rate was obtained from the equation shown by the following formula (1): &lt; EMI ID =

Imidation ratio (%) = {(1-A ¹ ) / (A ² × α)} × 100 (1)

(In Formula (1), A <^1> is the peak area derived from the proton of the NH group represented by 10 ppm of chemical shifts, A <^2> is the peak area derived from other protons, and (alpha) is a precursor (polyamic acid) of a polymer. Number ratio of other protons to one proton of NH group).

<Synthesis of polyorganosiloxane having an epoxy group>

Synthesis Example 1

100 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser tube And the mixture was mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise over 30 minutes from the dropping funnel, followed by reaction at 80 ° C. for 6 hours while mixing under reflux. After the completion of the reaction, the organic layer was taken out and washed with a 0.2% by mass ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group. Obtained as a clear liquid.

As a result of ¹ H-NMR analysis of the polyorganosiloxane having the epoxy group, a peak based on the epoxy group was obtained at a theoretical strength in the vicinity of chemical shift (δ) = 3.2 ppm, and no side reaction of the epoxy group occurred during the reaction. It was confirmed.

<Synthesis of Specific Carbonic Acid>

Specific carboxylic acid 1 was synthesized according to the following scheme.

[Synthesis Example 2]

To a 500 mL three-necked flask equipped with a cooling tube, 6.3 g of 4-cyano-4'-hydroxybiphenyl, 10 g of 11-bromodecanoate, 14.2 g of potassium carbonate, and 200 mL of N, N-dimethylformamide were added. It heated and stirred at 160 degreeC for 5 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was thrown into 500 mL of water, and the mixture was stirred. The precipitated white solid was filtered off and further washed with water. 11 g of compounds 1 were obtained by vacuum-drying the obtained solid at 80 degreeC.

[Synthesis Example 3]

Next, 10 g of compound 1, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol, and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 ° C. for 4 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. The precipitated solid was filtered and washed with water and ethanol in that order. 8g of specific carbonic acid 1 was obtained by vacuum-drying the obtained solid at 80 degreeC.

Specific carboxylic acid 2 was synthesized according to the following scheme.

[Synthesis Example 4]

To a 500 mL three-necked flask equipped with a cooling tube, 15 g of 4-cyano-4'-hydroxybiphenyl, 13.5 g of ethylene carbonate, 2.5 g of tetrabutylammonium bromide (TBAB), and 300 mL of N, N-dimethylformamide were added. It heated and stirred at 150 degreeC for 9 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was separated and washed with a mixed solution of 300 mL of ethyl acetate and 100 mL of an aqueous 1N-sodium hydroxide solution. After extracting the organic layer, the liquid was further separated and washed in order of 100 mL of 1N-sodium hydroxide aqueous solution and 100 mL of water. The organic layer was dried over magnesium sulfate, and then the organic solvent was distilled off. 13.1g of compounds 2 were obtained by vacuum-drying the obtained solid and recrystallizing with 100 mL of ethanol / 250 mL of hexane.

Synthesis Example 5

To a 200 mL three-necked flask equipped with a cooling tube and a dropping funnel, 12 g of Compound 2, 12.7 g of 4-chlorobenzenesulfonyl chloride, and 60 mL of dehydrated methylene chloride were added and mixed. In the state which cooled the reaction solution in the ice bath, the 10 mL solution of dehydration methylene chloride of 6.6g of triethylamine was dripped over 10 minutes. It stirred for 30 minutes in the ice bath state, returned to room temperature, and stirred for further 6 hours. 150 mL of chloroform was added to the reaction solution, and the liquid was washed four times with 100 mL of water. The extracted organic layer was dried over magnesium sulfate, and the organic solvent was distilled off. 16.1g of compound 3 was obtained by wash | cleaning the obtained solid with ethanol.

[Synthesis Example 6]

15 g of compound 3, 11 g of 4-hydroxybenzoate, 12.5 g of potassium carbonate, and 180 mL of N, N-dimethylformamide were added to a 300 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 ° C. for 9 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. The application liquid was poured into 500 mL of water, and mixed and stirred. The white solid precipitated was collected by filtration and washed further with ethanol. 10g of compounds 4 were obtained by vacuum drying the obtained solid at 80 degreeC.

[Synthesis Example 7]

To a 100 mL three-necked flask equipped with a cooling tube, 9.5 g of Compound 4, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol, 15 mL of tetrahydrofuran, and 15 mL of water were added, followed by heating and stirring at 80 ° C for 4 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. The precipitated solid was filtered and washed with water and ethanol in that order. 9g of specific carbonic acid 2 was obtained by vacuum-drying the obtained solid at 80 degreeC.

Specific carboxylic acid 3 was synthesized according to the following scheme.

[Synthesis Example 8]

In Synthesis Example 2, 13.7 g of 2,3,5,6-tetrafluoro-4- (pentafluorophenyl) phenol was used in place of 4-cyano-4'-hydroxybiphenyl to thereby make compound 5 13.7. g was obtained.

[Synthesis Example 9]

In Synthesis Example 3, 11.2 g of specific carboxylic acid 3 was obtained by using 13.5 g of Compound 5 instead of Compound 1.

Specific carboxylic acid 4 was synthesized according to the following scheme.

[Synthesis Example 10]

In Synthesis Example 4, compound 6 was used by using 25.5 g of 2,3,5,6-tetrafluoro-4- (pentafluorophenyl) phenol instead of 4-cyano-4'-hydroxybiphenyl. 23.1 g was obtained.

Synthesis Example 11

24.1g of compound 7 was obtained by using 18.9g of compound 6 instead of compound 2 in the synthesis example 5.

[Synthesis Example 12]

15.4g of compound 8 was obtained by using 20g of compound 7 instead of compound 3 in the synthesis example 6.

[Synthesis Example 13]

By using 13 g of compound 8 instead of compound 4 in Synthesis Example 7, 11.4 g of specific carboxylic acid 4 was obtained.

Specific carboxylic acid 5 was synthesized according to the following scheme.

[Synthesis Example 14]

15g of specific carbonic acid 5 which changed the number of methylene groups from 10 to 5 similarly to the synthesis of specific carbonic acid 1 was synthesize | combined.

Specific carboxylic acid 6 was synthesized according to the following scheme.

Synthesis Example 15

10.1 g of 2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl, 10 g of methyl 11-bromodecanoate and potassium carbonate in a 500 mL three-necked flask equipped with a cooling tube 14.2 g and 200 mL of N, N-dimethylformamide were added, and it stirred with heat at 160 degreeC for 5 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was thrown into 500 mL of water, and the mixture was stirred. It filtered and separated by the white solid which precipitated, and wash | cleaned further with water. 10.8g of compounds 9 were obtained by vacuum drying the obtained solid at 80 degreeC.

Synthesis Example 16

Next, 10 g of compound 9, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol, and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 ° C. for 4 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. The precipitated solid was filtered and washed with water and ethanol in that order. By vacuum drying the obtained solid at 80 degreeC, 6g of specific carbonic acid 6 was obtained.

 <Synthesis of Compound [A]>

Synthesis Example 17

In a 100 mL three-necked flask, 5.0 g of the specific carboxylic acid 1 obtained in 9.8 g of polyorganosiloxane having an epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, and Synthesis Example 3, represented by Formula (4) As one of the compounds, 3.3 g of 4-octyloxybenzoic acid represented by Formula (4-10) and 0.20 g of UCAT 18X (the quaternary amine salt of San Aprosa) were added and stirred at 80 ° C for 12 hours. After completion of the reaction, the precipitate was reprecipitated with methanol to dissolve the precipitate in ethyl acetate to obtain a solution. The solution was washed three times with water, and then the solvent was distilled off to give [A] Compound A-1 as a white powder. g was obtained. [A] Mw of the compound A-1 was 6,500.

Synthesis Example 18

The same procedure as in Synthesis Example 17 was repeated except that 4 g of the specific carboxylic acid 2 obtained in Synthesis Example 7 was used instead of the specific carboxylic acid 1 to obtain 12.8 g of a white powder of the compound [A] A-2. [A] Mw of the compound A-2 was 6,000.

Synthesis Example 19

Except having used 6.8 g of specific carboxylic acids 3 obtained by the synthesis examples 9 instead of specific carboxylic acids 1, it operated like a synthesis example 17 and obtained 14.7g of white powders of the [A] compound A-3. [A] Mw of the compound A-3 was 8,100.

Synthesis Example 20

Compound [A] was synthesized in the same manner as in Synthesis Example 17 except that 5.6 g of the specific carboxylic acid 4 obtained in Synthesis Example 13 was used instead of the specific carboxylic acid 1. As a result, 15.0 g of white powder of [A] compound A-4 was obtained. [A] Mw of the compound A-4 was 7,500.

Synthesis Example 21

In a 100 mL three-necked flask, 9.8 g of polyorganosiloxane having an epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 10 g of specific carbonic acid 1 obtained in Synthesis Example 3 and UCAT 18X (the fourth grade of San Aprosa) Amine salt) 0.20g was put, and it stirred at 80 degreeC for 12 hours. After the completion of the reaction, the precipitate was reprecipitated with methanol, the precipitate was dissolved in ethyl acetate, the solution was washed three times with water, and then the solvent was distilled off to obtain 16.0 g of [A] Compound A-5 as a white powder. [A] Mw of the compound A-5 was 8,500.

Synthesis Example 22

The same procedure as in Synthesis Example 21 was repeated except that 4.1 g of the specific carboxylic acid 5 obtained in Synthesis Example 14 was used instead of the specific carboxylic acid 1 to obtain 12.4 g of a white powder of the compound A-6. [A] Mw of the compound A-6 was 6,200.

Synthesis Example 23

Same as Synthesis Example 17 except that 3.6 g of 4- (4-pentylcyclohexyl) benzoic acid represented by Formula (4-11) exemplified as one of the compounds represented by Formula (4) instead of 4-octyloxybenzoic acid was used. 13.4g of white powders of [A] compound A-7 were obtained. [A] Mw of the compound A-7 was 7,900.

Synthesis Example 24

In a 100 mL three-necked flask, 8.0 g of the specific carbonic acid 1 obtained in Synthesis Example 3, 9.8 g of polyorganosiloxane having an epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, and Formula (4-11) 1.4 g of 4- (4-pentylcyclohexyl) benzoic acid and 0.20 g of UCAT 18X (the quaternary amine salt of San Apro) were added, and the mixture was stirred at 80 ° C for 12 hours. After the completion of the reaction, the precipitate was reprecipitated with methanol, the precipitate was dissolved in ethyl acetate, the solution was washed three times with water, and then the solvent was distilled off to obtain 13.9 g of [A] Compound A-8 as a white powder. [A] Mw of the compound A-8 was 8,900.

Synthesis Example 25

In a 100 mL three-necked flask, 9.8 g of polyorganosiloxane having an epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 2.0 g of specific carboxylic acid 1 obtained in Synthesis Example 3, formula (4-11) 5.8 g of 4- (4-pentylcyclohexyl) benzoic acid and 0.20 g of UCAT 18X (the quaternary amine salt of San Aprosa) were added, and it stirred at 80 degreeC for 12 hours. After the completion of the reaction, the precipitate was reprecipitated with methanol to dissolve the precipitate in ethyl acetate to obtain a solution. The solution was washed three times with water, and then the solvent was distilled off to give [A] Compound A-9 as a white powder. g was obtained. [A] Mw of the compound A-9 was 7,600.

Synthesis Example 26

18.4g of white powders of the compound [A] were obtained by operation similar to the synthesis example 24 except having used 6.1 g of the specific carboxylic acid 6 obtained by the synthesis example 16 instead of the specific carboxylic acid 1. [A] Mw of the compound A-10 was 7,300.

[Comparative Synthesis Example 1]

In a 100 mL three-necked flask, 9.8 g of polyorganosiloxane having an epoxy group obtained in Synthesis Example 1, 28 g of methyl isobutyl ketone, 3.3 g of 4-octyloxybenzoic acid, and 0.10 g of UCAT 18X (a quaternary amine salt of San Apro) Was added, and it stirred at 80 degreeC for 12 hours. After the completion of the reaction, the precipitate was reprecipitated with methanol, the precipitate was dissolved in ethyl acetate and the solution was washed three times with water, and then the solvent was distilled off to obtain 9.6 g of [A] compound CA-1 as a white powder. Mw of compound CA-1 was 6,000.

<Synthesis of polyamic acid>

Synthesis Example 27

As tetracarboxylic dianhydride, 11 g (0.05 mol) of pyromellitic dianhydrides, 190 g (0.95 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4-aminophenyl-4-aminobenzo as a diamine compound 160 g (0.71 mole), 4,4 '-[4,4'-propane-1,3-diylbis (piperidine-1,4-diyl)] dianiline 110 g (0.29 mole) was N-methyl- It was dissolved in 1300 g of 2-pyrrolidone (NMP) and 1300 g of γ-butyrolactone (γ-BL) and reacted at 40 ° C. for 6 hours to give a polyamic acid having a solid content concentration of 15% by mass and a solution viscosity of 420 mPa · s. A dark acid (PA-1) solution was obtained.

Synthesis Example 28

As tetracarboxylic dianhydride, 40 g (0.20 mol) of pyromellitic dianhydrides, 160 g (0.80 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydrides, 4-aminophenyl-4-aminobenzo as a diamine compound 140 g (0.62 mole), 4,4 '-[4,4'-propane-1,3-diylbis (piperidine-1,4-diyl)] dianiline 110 g (0.29 mole), diethylene glycol ( 26 g (0.09 mol) of di-4-aminophenyl) ether was dissolved in 1400 g of N-methyl-2-pyrrolidone (NMP) and 1400 g of γ-butyrolactone (γ-BL) and reacted at 40 ° C. for 6 hours. , 15 mass% of solid content concentration, and the polyamic acid (this is called polyamic acid (PA-2)) solution of solution viscosity 850 mPa * s were obtained.

Synthesis Example 29

As tetracarboxylic acid dianhydride 200 g (0.90 mol) of pyromellitic dianhydride, 22 g (0.10 mol) of 1,2,3,5-tricarboxycyclopentyl acetic acid dianhydrides, 22 g (0.50 mol) of p-phenylenediamines as a diamine compound ), 100 g (0.20 mol) of 4,4-diaminodiphenyl ether, 46 g (0.30 mol) of 3,5-diaminobenzoic acid, 1100 g of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone ( (gamma-BL) was dissolved in 1100 g, and reacted at 40 ° C for 4 hours to obtain a polyamic acid (this is called polyamic acid (PA-3)) solution having a solid content concentration of 15% by mass and a solution viscosity of 410 mPa · s.

<Synthesis of polyimide>

Synthesis Example 30

220 g (1.00 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 87 g (0.80 mol) of p-phenylenediamine as a diamine compound, 2,2'-bistrifluoromethyl- 32 g (0.10 mol) of 4,4'-diaminobiphenyl and 20 g (0.10 mol) of 4,4'-diamino diphenylmethane were dissolved in 2700 g of NMP, and reacted at 60 degreeC for 6 hours. A small amount of the obtained polyamic acid solution was collected, and NMP was added thereto, and the viscosity was measured by a solution having a solid content concentration of 10% by mass, and the result was 35 mPa · s. Subsequently, 2200 g of NMP were added to the obtained polyamic acid solution, 160 g of pyridine and 200 g of acetic anhydride were added, and the dehydration ring was closed at 110 degreeC for 4 hours. After the imidization reaction, the solvent in the system was solvent-substituted with fresh NMP (pyridin and acetic anhydride used in the imidation reaction in this operation were removed to the outside of the system), and polyimide (PI-1) having an imidation ratio of about 78% was removed. The solution containing about 15 mass% was obtained. The obtained polyimide solution was fractionated and the solution viscosity measured as a solution of 6.5 mass% of polyimide concentration by adding NMP was 13 mPa * s.

Synthesis Example 31

220 g (1.00 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 110 g (1.00 mol) of p-phenylenediamine as a diamine compound are dissolved in 3000 g of NMP, and 4 hours at 60 ° C. Reacted. A small amount of the obtained polyamic acid solution was added, and NMP was added thereto and the viscosity was measured using a solution having a solid content concentration of 10% by mass, and the result was 68 mPa · s. Next, 3300 g of NMP was added to the obtained polyamic acid solution, 400 g of pyridine and 310 g of acetic anhydride were added, and it was dehydrated and closed for 4 hours at 110 degreeC. After the imidization reaction, the solvent in the system was solvent-substituted with fresh NMP (pyridin and acetic anhydride used in the imidation reaction in this operation were removed to the outside of the system), and polyimide (PI-2) having an imidation ratio of about 88% was removed. The solution containing about 11 mass% was obtained. The obtained polyimide solution was fractionated and the solution viscosity measured as a solution of polyimide concentration 6.8 mass% by adding NMP was 32 mPa * s.

&Lt; Preparation of liquid crystal aligning agent &

Example 1

The solution containing the polyamic acid (PA-1) obtained in the synthesis example 27 was converted into the polyamic acid (PA-1) contained in this, and the quantity equivalent to 1,000 mass parts is taken, and [A] compound A-1 ( 100 parts by mass), and further-gamma -butyrolactone, N-methyl-2-pyrrolidone and butyl cellosolve, the solvent composition is gamma -butyrolactone: N-methyl-2-pyrrolidone : Butyl cellosolve = 40:40:20 (mass ratio), It was set as the solution whose solid content concentration is 4.0 mass%. Liquid crystal aligning agent S-1 was prepared by filtering this solution with the filter of 0.45 micrometers of pore diameters.

[Examples 2 to 14 and Comparative Examples 1 to 4]

[B] The same procedure as in Example 1 was carried out except that the combination of the polyamic acid or polyimide as the polymer and the polyorganosiloxane compound as the [A] component were as described in Table 1, and the liquid crystal aligning agents S-2 to S-14 and CS-1 to 4 were prepared.

[Example 15]

The solution containing the polyimide (PI-1) obtained by the synthesis example 30 was converted into the polyimide (PI-1) contained in this, and it contains 800 mass parts and the polyamic acid (PA-3) obtained by the synthesis example 29. The solution to make is converted into the polyamic acid (PA-3) contained in this, takes the quantity equivalent to 200 mass parts, [A] compound A-1 (100 mass parts) is added, and (gamma) -butyrolactone is further added , N-methyl-2-pyrrolidone and butyl cellosolve were added, and the solvent composition was (gamma) -butyrolactone: N-methyl-2-pyrrolidone: butyl cellosolve = 40: 40: 20 (mass ratio) Solid content concentration was made into the solution which is 4.0 mass%. Liquid crystal aligning agent S-15 was prepared by filtering this solution with the filter of 0.45 micrometers in diameter.

Example 16, Comparative Example 5

[B] The same procedure as in Example 15 was conducted except that the combination of the polyamic acid and the polyimide as the polymer and the polyorganosiloxane compound as the [A] component were as described in Table 1, to obtain a liquid crystal aligning agent S-16, CS-5 was prepared.

<Manufacture of Liquid Crystal Display Element>

As a liquid crystal display element using the liquid crystal aligning agent S-1, the schematic diagram of the board | substrate with which the patterned electrode pair was provided was shown to FIG. As the substrate on the opposite side, flat glass without an electrode film was used.

On these board | substrates, a liquid crystal aligning film is formed using a liquid crystal aligning agent S-1 by spin coating method, and it is 230 degreeC * 5 minutes (70 degreeC * 80 second on a hotplate as a prebaking, and a clean oven as postbaking in a clean oven) Baking was carried out under nitrogen). Furthermore, the rubbing process was performed with cotton in the direction shown in FIG. These board | substrates were bonded together through the spacer of 3.5 micrometers in diameter so that the rubbing direction of each board | substrate might be reversed, and the empty cell of liquid crystal non-injection was produced. A liquid crystal MLC-6221 (manufactured by Merck Co.) was injected into this cell. Furthermore, the liquid crystal display element of Example 1 was produced by bonding the polarizing plate to the outer both surfaces of a board | substrate so that the polarization direction of two polarizing plates may mutually orthogonally cross.

Except having used the liquid crystal aligning agent shown in Table 1 instead of liquid crystal aligning agent S-1, operation similar to the above was performed and the liquid crystal display element using the liquid crystal aligning agent of Examples 2-16 and Comparative Examples 1-5 was created. .

<Evaluation>

The following evaluation was performed about the manufactured liquid crystal display element. The results are shown together in Table 1.

[Orientation]

About the liquid crystal display element manufactured above, the presence or absence of the light leakage and orientation disorder in the voltage-free state is observed by visual observation under backlight irradiation, and it is set as "(circle)" when there is no light leakage and orientation disorder, The case where light leakage and orientation disturbance existed in was set as "(triangle | delta)", and it was set to "x" that the vertical alignment state was not obtained at all.

Response speed (electro-optic response at startup)

The start time of a liquid crystal response was measured with the apparatus containing a polarizing microscope, a light detector, and a pulse generator. Here, liquid crystal response speed was made into the time (msec.) Required for changing from 10% of transmittance to 90% of the transmittance | permeability when voltage of 5V is applied to the produced liquid crystal display element for a maximum of 1 second from a voltage-free state. .

As will be apparent from the results in Table 1, the liquid crystal display element provided with the liquid crystal aligning film produced using the liquid crystal aligning agent of Examples 1-16 is excellent in orientation, and about the response speed of a liquid crystal, the liquid crystal display element of a comparative example Compared with that, it was found that the speed was increased to about 3/4 or more.

The liquid crystal aligning agent of this invention can be used suitably for manufacture of the liquid crystal display element of IPS and FFS system excellent in high-speed response.

Claims (7)

As a liquid crystal aligning agent for liquid crystal aligning film formation in the liquid crystal display element of IPS and FFS system,
[A] A liquid crystal aligning agent containing a compound having a group represented by the following formula (1):

(In formula (1), R ¹ is a group having at least two monocyclic structures; R ² is a linking group containing a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom; a is 0 to 1) Is an integer of). The method of claim 1,
[A] The compound is,
A part derived from a polyorganosiloxane having an epoxy group,
Liquid crystal aligning agent which has a part derived from the compound which has a carboxyl group represented by following formula (2):

(In formula (2), R <^1> , R <^2> and a are the same meaning as said Formula (1); R <^3> is a methylene group or a C2-C30 alkylene group, a phenylene group, or a cyclohexylene group, These The group may further have a substituent). The method of claim 1,
Liquid crystal aligning agent in which said R <^1> is group represented by following formula (3):

(In formula (3), R ⁴ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group or an alkoxy group; R ⁵ and R ⁷ are each independently a phenylene group, a biphenylene group, naphthalene group, a cyclohexylene group, a bi-cyclohexylene group, a cyclohexylene group and the phenyl or heterocyclic ring, these groups may further have a substituent; R ⁶ is an alkylene group, a double bond of 1 to 10 carbon atoms, 3 A linking group including any of a heavy bond, an ether bond, an ester bond, and a heterocycle, and these groups may further have a substituent; b is an integer of 1 to 9; when b is 2 or more, a plurality of R ⁴ are the same C is an integer of 0-1, d is an integer of 1-2, and when d is 2, some R <^6> and R <^7> may be same or different, respectively). 3. The method of claim 2,
Wherein the epoxy group, the formula (X ¹ -1) or a group represented by a liquid crystal alignment (X ¹ -2) claim:

(In formula (X ^1-1 ), A is an oxygen atom or a single bond; h is an integer of 1 to 3; i is an integer of 0 to 6; provided that when i is 0, A is a single bond; ; formula (X ¹ -2) of the, j is an integer of 0 to 6). 5. The method according to any one of claims 1 to 4,
(B) The liquid crystal aligning agent which further contains at least 1 sort (s) of polymer chosen from the group which consists of a polyamic acid and a polyimide. The liquid crystal display element of the IPS and FFS system provided with the liquid crystal aligning film formed from the liquid crystal aligning agent in any one of Claims 1-4. The liquid crystal display element of IPS and FFS system provided with the liquid crystal aligning film formed from the liquid crystal aligning agent of Claim 5.

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